JP2011006667A - Water-repellent film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a super water-repellent film comprising a polymer having a fine surface structure (rugged structure), in particular, a method for producing a super water-repellent film on the basis of a phase separation phenomenon of a polymer caused by a polymerization reaction induced by energy ray irradiation, and an ultra water-repellent film formed by the production method.SOLUTION: The method for producing the ultra water-repellent film includes the steps of: producing a film-forming composition (X) obtained by mixing together a polymerizable compound (A) that is polymerizable by energy ray irradiation, a compound (B) that is compatible with the polymerizable compound (A) but incompatible with a polymerized polymer (P) thereof and is inactive to energy ray, and a polymer (C) that is compatible with the polymerizable compound (A) but only partially compatible with the polymerized polymer (P) and is inactive to energy ray; forming a layer of the film-forming composition (X); and removing the compound (B) after polymerizing the polymerizable compound (A) by energy ray irradiation.

Description

  The present invention relates to a water-repellent film and a method for producing the same, and more particularly to a water-repellent film made of a polymer having a fine concavo-convex structure on the surface and a method for producing the same.

  In recent years, a surface that repels water very strongly (super water-repellent surface) has attracted attention. Although there is no scientific definition of a super water-repellent surface, it generally refers to a surface that has a water contact angle of 150 ° or more and is extremely difficult to wet. Since the super water-repellent surface can significantly reduce the contact area with water, the progress of various chemical reactions and the formation of chemical bonds via water can be suppressed. For this reason, higher effects can be expected compared to conventional water-repellent surfaces (water contact angles of about 90 to 120 °) for various purposes such as antifouling, rust prevention, snowdrop prevention, and electrical insulation. The range of applications includes exteriors and interiors of housing and automobiles, interiors of residential waters such as kitchens, bathrooms, and washrooms, electrical appliances, leather products such as shoes and bags, clothing including sports applications, medical instruments, and dentistry. It covers a wide range of equipment, and other outdoor equipment such as steel towers, antennas, and electric wires, and surface coating materials such as household goods such as umbrellas, raincoats, helmets, paper, curtains, and carpets.

  Incidentally, in the technical field of water repellent materials, as described above, a surface having a water contact angle of approximately 150 ° or more is referred to as a super water repellent surface, and a surface exhibiting a water contact angle in the range of approximately 120 to 150 ° is a highly water repellent surface. A surface showing a water contact angle in the range of approximately 90 to 120 ° is referred to as a normal water-repellent surface.

  The wetting phenomenon of a solid surface is determined by the surface chemistry and roughness (geometric morphology, topology). Therefore, if both of them can be skillfully controlled, a surface having a desired wettability can be obtained. The super water-repellent film can be realized by imparting a fine structure (uneven structure) to a surface made of a low energy material. In order to obtain a super water-repellent film, many surface fine structure forming means have been taken so far, and among them, a method utilizing a phase separation phenomenon between substances, particularly a polymer phase separation phenomenon, Although there are few examples, it is excellent in terms of manufacturing simplicity.

  In Patent Document 1, a base material surface is coated with a polymer network structure in which a low molecular organic material is held between three-dimensional continuous network skeletons composed of a thermoplastic elastomer material melted at high temperature, and then cooled. The polymer / low molecular phase separation state was formed, and the low molecular component was removed by solvent extraction to form a fine concavo-convex structure on the film surface. The film thus obtained showed a water contact angle of 150 ° or more, indicating that it was a super water-repellent film.

  In Non-Patent Document 1, isotactic polypropylene (i-PP) is dissolved in a mixed solvent (including a good solvent and a non-solvent for i-PP) and then cast on a substrate at a relatively high temperature. Then, by controlling the evaporation process of the solvent, a phase separation state was induced, and an i-PP film having a fine concavo-convex structure was formed. The water contact angle value of this membrane was about 160 °.

  In the inventions of the above two examples, the phase separation state between the polymer material and the low molecular weight material or the solvent can be achieved by passing through the high temperature state of the mixture, and a relatively complicated operation is required to obtain a super water-repellent film. I need.

  On the other hand, in Patent Document 2 and Non-Patent Document 2, a composition comprising a monomer that can be polymerized by irradiation with energy rays, an oligomer or polymer that is inert to energy rays, and a solvent is coated on the surface of the substrate. By irradiating energy rays to polymerize the monomer, a phase separation state is induced in the temperature range near room temperature, and from this, the oligomer or polymer and solvent are removed to form a polymer film having a fine concavo-convex structure. . However, these are mainly inventions using highly hydrophilic monomers and are not inventions intended to form a super water-repellent film.

  In Patent Document 3, ultraviolet curing and heat curing are performed on a coating film made of a mixed coating material having an acrylic ultraviolet polymerization curing coating, a silicone-based abrasion-resistant thermal polymerization curing coating, and a silane coupling agent having fluorine. Although the water repellent film is obtained by the combined use, the water contact angle value on the film surface is 98 ° at the maximum, and it does not show super water repellency.

JP 2005-53104 A JP 05-271460 A Japanese Unexamined Patent Publication No. 08-169968

H. Y. Erbil et al., Science, 2003, 299, 1377-1380. R. H. Schmidt et al., Chem. Mater., 2005, 17, 1007-1016.

  The problem to be solved by the present invention is to provide a water-repellent film by a simple and normal temperature process, particularly a super-water-repellent film having a water contact angle of 150 ° or more, utilizing the phase separation phenomenon of a polymer caused by a polymerization reaction caused by energy beam irradiation. And a super water-repellent film formed by the manufacturing method.

  As a result of various studies, the present inventors have found that a layer of a film-forming composition in which a polymerizable compound that can be polymerized by irradiation with energy rays and an additive that is inert to energy rays is mixed is formed on a substrate. It was formed and polymerized by irradiation with energy rays to induce a phase separation state, and then it was found that the above problems could be solved by removing a part of the soluble additive, and the present invention was completed.

That is, the present invention comprises a polymerizable compound (A) that can be polymerized by irradiation with energy rays,
A compound (B) that is compatible with the polymerizable compound (A) but is not compatible with the polymer polymer (P _A ) of the polymerizable compound ( _A ) and is inactive with respect to energy rays. ,
A step of producing a film-forming composition (X) in which the polymerizable compound (A) and the compound (B) are compatible with each other and a polymer (C) that is inert to energy rays is mixed;
Forming a layer of the film-forming composition (X);
A method for producing a water-repellent film comprising the step of polymerizing the polymerizable compound (A) in the film-forming composition (X) by irradiation with energy rays and then removing the compound (B). provide.

  The present invention also provides a water-repellent film produced by the above production method.

  Furthermore, the present invention provides a polymer of a polymerizable compound (A) that can be polymerized by irradiation with energy rays, and a polymer (C) that is compatible with the polymerizable compound (A) and is inert to energy rays. And having a mean surface roughness (Ra) of more than 30 nm and up to 1000 nm.

  According to the production method of the present invention, a film-forming composition comprising a polymerizable compound that can be polymerized by irradiation with energy rays without handling the resin melted at a high temperature disclosed in Patent Document 1 and Non-Patent Document 1. By the energy ray curing of the coating film, a water-repellent film can be produced by a simple and normal temperature process. Further, according to the production method of the present invention, a polymer thin film having a surface fine structure and a thickness of 1.0 μm or less can be easily obtained, and a highly transparent water-repellent film can be provided.

2 is a photograph of water droplets on the surface of the super water-repellent film [SH-1] obtained in Example 1. 2 is a scanning electron microscope image of the surface of a super water-repellent film [SH-1] obtained in Example 1. FIG. 2 is an atomic force microscope image on the surface of a super water-repellent film [SH-1] obtained in Example 1. It is a water droplet photograph on the surface of the super water-repellent film [SH-14] obtained in Example 14. It is a scanning electron microscope image of the surface of the super water-repellent film [SH-14] obtained in Example 14. It is an atomic force microscope image on the surface of the super water-repellent film [SH-14] obtained in Example 14. 4 is a photograph of water droplets on the surface of the super water-repellent film [SH-16] obtained in Example 16. 16 is a scanning electron microscope image of the surface of a super water-repellent film [SH-16] obtained in Example 16. 6 is an atomic force microscope image on the surface of a super water-repellent film [SH-16] obtained in Example 16.

  The present invention will be described below.

  In the technical field of water repellent materials, there is no scientific distinction and definition in terms of science, but in general, a surface having a water contact angle of approximately 150 ° or more is referred to as a super water repellent surface, and approximately 120 A surface showing a water contact angle in the range of ˜150 ° is called a highly water-repellent surface, and a surface showing a water contact angle in the range of about 90-120 ° is distinguished from a normal water-repellent surface.

  In the present specification, the above general distinction is adopted, and a surface having a water contact angle of 150 ° or more is defined as a “super-water-repellent” surface, and indicates a water contact angle in a range of 120 ° to less than 150 °. A surface is defined as a “high water repellency” surface, and a surface exhibiting a water contact angle in the range of 90 ° to less than 120 ° is defined as a “normal water repellency” surface. However, the simple description of “water-repellent surface” includes all of “super-water-repellent surface”, “highly water-repellent surface” and “normal water-repellent surface”.

  In the production method of the present invention, control is performed by selection of raw materials, adjustment of blending amount, adjustment of film formation conditions, etc., until production of a film having “super water repellency”, “high water repellency” and “normal water repellency” Although possible, it is particularly suitable for the production of membranes having “super water repellency” and “high water repellency” surfaces, and is most suitable for the production of membranes having “super water repellency” surfaces. Therefore, the following description will be mainly focused on a method for manufacturing a film having a super water-repellent surface.

The super water-repellent film of the present invention is compatible with the polymerizable compound (A) that can be polymerized by irradiation with energy rays and the polymerizable compound (A), but the polymer compound of the polymerizable compound (A) ( P _A ) is not compatible with the compound (B) which is inactive with respect to the energy rays, and is compatible with the polymerizable compound (A) and the compound (B) and with respect to the energy rays. A thin layer of the film-forming composition (X) mixed with an inert polymer (C) is formed, polymerized by irradiation with energy rays, and then removed by removing the compound (B). .

In this method, the polymer polymer (P _A ) produced by polymerization of the polymerizable compound (A) becomes incompatible with the compound (B), and the phase separation between the polymer polymer (P _A ) and the compound (B) occurs. state occurs, the polymer polymer (P _a) or inside the polymer a polymer (P _a) compounds during (B) is in a state incorporated. By removing the compound (B), the region occupied by the compound (B) becomes pores, and a fine concavo-convex structure is induced on the film surface, so that a super water-repellent film can be formed. The polymer (C) may be completely removed from the cured film of the film-forming composition (X) as long as the effects of the present invention are not impaired. However, at least one of the polymers (C) is required for ensuring the strength of the cured film. It is preferable to leave the part in the cured film. Therefore, in the phase separation state of the polymer polymer (P _A ) and the compound (B), the polymer (C) is preferably distributed to some extent in the polymer polymer (P _A ) phase, and the higher the distribution ratio, the higher The higher the strength of the cured film is.

  As the polymerizable compound (A), a polymerizable compound (a) that can be polymerized by irradiation with energy rays can be used as a single component or a mixture of two or more thereof. The polymerizable compound (a) is not particularly limited as long as it is a substance that is polymerized by irradiation with energy rays and becomes a polymer, and may be any one such as radical polymerizable, anionic polymerizable, and cationic polymerizable. For example, a polymerizable compound containing a vinyl group is used, and among them, a (meth) acrylic compound having a high polymerization rate by irradiation with energy rays is preferable. Further, since the strength after curing can be increased, the compound is preferably a compound that forms a crosslinked polymer by polymerization, and is particularly preferably a bifunctional or more polymerizable compound having two or more vinyl groups in one molecule. preferable.

  Examples of the (meth) acrylic compound include ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di. (Meth) acrylate, neopentyl glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, glycerin di (meth) acrylate, 2- Isocyanato-2-methylpropyl di (meth) acrylate, 2-methacryloyloxyethyl acid phosphate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanedioe Di (meth) acrylate, 2,2'-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, 2,2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane, hydroxydipivalic acid Bifunctional monomers such as neopentyl glycol di (meth) acrylate, dicyclopentanyl diacrylate, bis (acryloxyethyl) hydroxyethyl isocyanurate, N-methylenebisacrylamide; trimethylolpropane tri (meth) acrylate, trimethylolethane Trifunctional compounds such as tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate Mer; tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate; hexafunctional monomers such as dipentaerythritol hexa (meth) acrylate.

  Examples of the polymerizable oligomer having a (meth) acryloyl group in the molecular chain include those having a weight average molecular weight of 500 to 50,000. For example, (meth) acrylic acid ester of epoxy resin, ( (Meth) acrylic acid ester, (meth) acrylic acid ester of polyether resin having bisphenol A skeleton, (meth) acrylic acid ester of polybutadiene resin, (meth) acrylic acid ester of polydimethylsiloxane resin, (meth) at the molecular end Examples thereof include a polyurethane resin having an acryloyl group.

  Among the above-mentioned polymerizable compounds and polymerizable oligomers, ethylene glycol di (meth) acrylate is highly hydrophobic and has a high crosslinking density after polymerization and is easy to give a polymer film having a developed surface microstructure. 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate is preferably used.

  Moreover, as the polymerizable compound (a), a monofunctional polymerizable compound having one vinyl group, particularly a (meth) acrylic compound having one vinyl group can be used. However, the monofunctional polymerizable compound is preferably used together with a bifunctional or higher polymerizable compound.

  Examples of (meth) acrylic compounds having one vinyl group include methyl (meth) acrylate, alkyl (meth) acrylate, isobornyl (meth) acrylate, alkoxy polyethylene glycol (meth) acrylate, phenoxydialkyl (meth) acrylate, Phenoxypolyethylene glycol (meth) acrylate, alkylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol acrylate methacrylate, butanediol mono (meth) acrylate, 2-hydroxy-3 -Phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl acrylate, Tylene oxide modified phthalic acid acrylate, ω-carboxycaprolactone monoacrylate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxyethyl succinic acid, acrylic acid dimer, 2-acryloyloxypropyl hexahydrohydrogen phthalate, fluorine-substituted alkyl ( (Meth) acrylate, chlorine-substituted alkyl (meth) acrylate, sulfonic acid sodaethoxy (meth) acrylate, sulfonic acid-2-methylpropane-2-acrylamide, phosphoric ester group-containing (meth) acrylate, glycidyl (meth) acrylate, 2- Isocyanatoethyl (meth) acrylate, (meth) acryloyl chloride, (meth) acrylaldehyde, sulfonate group-containing (meth) acrylate , Silano group-containing (meth) acrylate, ((di) alkyl) amino group-containing (meth) acrylate, quaternary ((di) alkyl) ammonium group-containing (meth) acrylate, (N-alkyl) acrylamide, (N, N -Dialkyl) acrylamide, acryloylmorpholine, polydimethylsiloxane chain-containing (meth) acrylate and the like.

  Among these monofunctional polymerizable compounds, methyl (meth) acrylate, alkyl (meth) acrylate, and isobornyl (meth) acrylate are also used on the film surface after polymerization for the purpose of increasing hydrophobicity and adjusting viscosity. Fluorine-substituted alkyl (meth) acrylate, polydimethylsiloxane chain-containing (meth) acrylate, and the like are preferably used for the purpose of uneven distribution and lowering the free energy of the surface.

As the compound (B), the compound (D) can be used as a single component or as a mixture of two or more thereof. Compound (D) is compatible with the polymerizable compound (A) as a component of the compound (B), but is not compatible with the polymer polymer (P _A ) of the polymerizable compound (A), and There is no particular limitation as long as it is inert to energy rays. However, the compound (B) stays on the substrate in the polymerization process of the polymerizable compound (A), and is removed mainly by washing with a solvent after the polymerization of the polymerizable compound (A), and the surface microstructure is reduced. Since it is necessary to provide the super water-repellent film having the compound (D), the compound (D) is preferably a compound having low volatility and high solubility in a solvent. Therefore, the compound (D) is preferably a liquid or solid having a molecular weight of 500 or less and a saturated vapor pressure at 25 ° C. of 600 Pa or less. The molecular weight is more preferably 300 or less. Furthermore, when the compound (D) is a highly hydrophobic compound, it exists in the vicinity of the surface when forming a phase separation state with the polymer polymer (P _A ), and after removal, a fine uneven structure is induced on the film surface. It is preferable because it is easy to form a super water-repellent film. Therefore, the compound (b) is preferably a compound that does not contain a polar chemical unit such as a hydroxyl group, an amino group, a carboxy group, an isocyanate group, a mercapto group, a cyano group, an amide bond, and a urea bond.

  As a highly hydrophobic compound that satisfies such requirements, the compound (D) is a compound represented by the formula (1), the formula (2), the formula (3), and the formula (4), and An alkane having 10 to 20 carbon atoms which may be branched is exemplified.

（式（１）中、Ｒ_１は炭素数が７〜１９の分岐していてもよいアルキル基又はベンジル基、Ｒ_２はメチル基又はエチル基を表す。）

(In the formula (1), R ₁ represents an alkyl group or benzyl group having 7 to 19 carbon atoms, and R ₂ represents a methyl group or an ethyl group.)

（式（２）中、Ｒ_３はメチル基又はエチル基、Ｒ_４は炭素数８〜２０の分岐していてもよいアルキル基又はベンジル基を表す。）

(In Formula (2), R ₃ represents a methyl group or an ethyl group, and R ₄ represents an alkyl group having 8 to 20 carbon atoms which may be branched or a benzyl group.)

（式（３）中、Ｒ_５〜Ｒ_１０は、それぞれ独立して水素原子又は分岐していてもよいアルキル基を表すが、そのうちの少なくとも２つがエチル基であるか、少なくとも１つが炭素数３〜８の分岐していてもよいアルキル基である。）

(In formula (3), R _{5 to} R ₁₀ each independently represents a hydrogen atom or an optionally branched alkyl group, and at least two of them are ethyl groups, or at least one of them has 3 carbon atoms. -8 alkyl groups which may be branched.)

（式（４）中、Ｒ_１１及びＲ_１２は、それぞれ独立して炭素数２〜８の分岐していてもよいアルキル基を表す。）

(In Formula (4), R ₁₁ and R ₁₂ each independently represents an alkyl group having 2 to 8 carbon atoms which may be branched.)

In Formula (1) and Formula (2), R ₁ and R ₄ are preferably an alkyl group having 7 to 18 carbon atoms, and more preferably an 8 to 16 alkyl group. In formula (3), at least one of R _{5 to} R ₁₀ is preferably an alkyl group having 3 to 7 carbon atoms, and more preferably an alkyl group having 3 to 6 carbon atoms. In this case, the remaining other groups are preferably hydrogen atoms. _Further, it is preferable that the total number of carbon atoms in R 5 _{to R 10} is 10 or less. Furthermore, in formula (4), R ₁₁ and R ₁₂ are each independently preferably an alkyl group having 2 to 7 carbon atoms, and more preferably an alkyl group having 2 to 6 carbon atoms. The alkane is preferably an alkane having 12 to 20 carbon atoms, and more preferably an alkane having 12 to 18 carbon atoms.

  Among these, when a liquid or solid having a saturated vapor pressure at 25 ° C. of 150 Pa or less is used, a thin film can be formed because of its low volatility, and a highly transparent super water-repellent film is produced. It is advantageous to do. As such a compound, methyl esters of long-chain aliphatic carboxylic acids such as methyl tetradecanoate, methyl hexadecanoate and methyl octadecanoate are preferably used.

Moreover, coexistence of the highly volatile liquid compound (E) as a constituent component together with the compound (D) in the compound (B) reduces the film thickness of the superhydrophobic film to be prepared. Useful for increasing transparency. In this case, after coating the film-forming composition on the substrate, the compound (D) remains on the substrate through the polymerization process of the polymerizable compound (A), whereas the compound (E) volatilizes. As a result, the film thickness is reduced. Such a compound (E) is preferably a liquid having a saturated vapor pressure at 25 ° C. of 600 Pa or more. As a highly hydrophobic compound that satisfies such requirements, pentane, hexane, heptane, R ₁₃ COOR ₁₄ (wherein R ₁₃ and R ₁₄ each independently represents an alkyl group having 1 to 5 carbon atoms). The total number of carbon atoms of R ₁₃ and R ₁₄ is 6 or less.), R ₁₅ COR ₁₆ (wherein R ₁₅ and R ₁₆ each independently represents an alkyl group having 1 to 5 carbon atoms). , R ₁₅ and R ₁₆ have a total carbon number of 6 or less.), R ₁₇ OR ₁₈ (wherein R ₁₇ and R ₁₈ each independently represents an alkyl group having 1 to 6 carbon atoms, The total number of carbon atoms of ₁₇ and R ₁₈ is 7 or less.), Benzene, toluene, dichloromethane, chloroform, and carbon tetrachloride are preferably used. Specific examples of R ₁₃ COOR ₁₄ include ethyl acetate, methyl propionate, ethyl propionate, methyl butanoate, ethyl butanoate, methyl pentanoate, ethyl pentanoate, methyl hexanoate and the like. Specific examples of R ₁₅ COR ₁₆ As acetone, methyl ethyl ketone, methyl isobutyl ketone and the like, and specific examples of R ₁₇ OR ₁₈ include diethyl ether.

  The mixing ratio of the compound (D) and the compound (E) can be appropriately set at an arbitrary ratio depending on the target performance of the super water-repellent film, particularly transparency.

As the polymer (C), a polymer can be used as a single component or a mixture of two or more thereof. As a constituent component of the polymer (C), there is no particular limitation as long as it is compatible with the polymerizable compound (A) and the compound (B) and is inactive with respect to energy rays. The polymer (C) may be completely removed from the cured film of the film-forming composition (X) as long as the effects of the present invention are not impaired. However, at least one of the polymers (C) is required for ensuring the strength of the cured film. It is preferable to leave the part in the cured film. Therefore, in the phase separation state of the polymer polymer (P _A ) and the compound (B), the polymer (C) is preferably distributed to some extent in the polymer polymer (P _A ) phase, and the higher the distribution ratio, the higher The higher the strength of the cured film is. From such a viewpoint, the polymer (C) is preferably highly hydrophobic because it becomes a component constituting the super water-repellent film, and an acrylic (co) polymer or a styrene (co) polymer is preferably used. It is done. Among them, polymethyl (meth) acrylate, polyethyl (meth) acrylate, polyisopropyl (meth) acrylate, polybutyl (meth) acrylate, polyisobutyl (meth) acrylate, poly tert-butyl (meth) acrylate, polyhexyl (meth) acrylate, polydodecyl (Meth) acrylate, polystearyl (meth) acrylate, polyisobornyl (meth) acrylate, polystyrene, and poly α-methylstyrene are particularly preferably used. One of the roles of the polymer (C) is to expand the phase separation conditions by increasing the viscosity of the film-forming composition (X). That is, the higher the viscosity of the film-forming composition (X), the more types of polymerizable compounds (A) and compounds (B) that can be used in the composition. Further, as will be described later, the viscosity of the film-forming composition (X) affects the pore diameter and surface irregularity of the super water-repellent film. Therefore, it is important that the molecular weight of the polymer is appropriately set according to the target performance of the super water-repellent film. The molecular weight of the polymer is preferably set in the range of 10,000 to 1,000,000.

  Depending on the relative contents of the polymerizable compound (A), the compound (B) and the polymer (C) contained in the film-forming composition (X), the pore diameter, surface irregularity and strength of the super water-repellent film change. As the content of the polymerizable compound (A) increases, the strength of the film improves, but the pore diameter and surface irregularities inside the film become smaller, and the water repellency tends to decrease. The preferable content of the polymerizable compound (A) is in the range of 30 to 80% by mass, particularly preferably in the range of 40 to 70% by mass. When the content of the polymerizable compound (A) is 30% by mass or less, the strength of the film is lowered, and when the content of the polymerizable compound (A) is 80% by mass or more, the pore diameter and surface unevenness inside the film are adjusted. Becomes difficult.

  The viscosity of the film forming composition (X) affects the pore shape of the film. When the film-forming composition (X) has a low viscosity, the shape of the pores is often given as a gap between the granular polymers adhered to each other. Often given. That is, the higher the viscosity, the better the coatability and the uniformity of the film thickness, but the pore diameter and surface irregularities become finer and the water repellency tends to decrease. Accordingly, the relative content of the polymerizable compound (A), the compound (B) and the polymer (C), the relative content of the polymer (C) with respect to the compound (B), depending on the target performance of the super water-repellent film such as transparency. It is important to appropriately set the viscosity of the film-forming composition (X) by changing.

  In the film-forming composition (X), a polymerization initiator, a polymerization inhibitor, a polymerization retarder, a thickener, etc. are used to adjust the polymerization rate and degree of polymerization, the pore diameter of the film, the surface irregularity, etc. Various additives may be added.

  The polymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound (A) by irradiation with energy rays, and includes a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, and the like. Can be used. For example, acetophenones such as p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, 4,4′-bisdimethylamino Ketones such as benzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, hydroxy Benzyl ketals such as cyclohexyl phenyl ketone, and azides such as N-azidosulfonylphenylmaleimide. A polymerizable photopolymerization initiator such as a maleimide compound can also be used. Further, the polymerization initiators listed here are disulfide compounds such as tetraethylthiilam disulfide, nitroxide compounds such as 2,2,6,6-tetramethylpiperidine-1-oxyl, 4,4′-di-t- It can also be used as a living radical polymerization initiator in combination with a compound such as butyl-2,2′-bipyridine copper complex-methyl trichloroacetate complex or benzyldiethyldithiocarbamate.

  Examples of the polymerization retarder and polymerization inhibitor include vinyl monomers having a low polymerization rate such as α-methylstyrene and 2,4-diphenyl-4-methyl-1-pentene, and hindant phenols such as tert-butylphenol. .

  As the thickener, known and commonly used thickeners can be used for the purpose of improving the coating property and the uniformity of the film thickness, and for controlling the pore diameter inside the film and the unevenness of the surface. As described above, since the viscosity of the film-forming composition (X) affects the pore shape of the film, it increases depending on the combination of materials constituting the film-forming composition (X) and the target performance of the film. It is important to select a sticky agent and set the amount used appropriately.

  The water-repellent film in the present invention may be a self-supporting film of a single film, but can be used as a laminate laminated with a base material (S). The base material (S) to be laminated with the water-repellent film of the present invention is not substantially affected by the film-forming composition (X) or the energy rays used, for example, dissolution, decomposition, polymerization, etc. do not occur, and Any film that does not substantially invade the film-forming composition (X) may be used. Examples of such a substrate include resins, crystals such as glass and quartz, semiconductors such as ceramics and silicon, metals, and metal oxides. Among these, high transparency and low cost Therefore, a resin or glass is preferable. The resin used for the substrate may be a single-monomer polymer polymer, a multi-monomer copolymer polymer, a thermoplastic polymer, or a thermosetting polymer. . The substrate may be composed of a polymer blend or a polymer alloy, or may be a laminate or other complex. Furthermore, the base material may contain additives such as a modifier, a colorant, a filler, and a reinforcing material.

  The shape of the substrate is not particularly limited, and any shape can be used according to the purpose of use. For example, a sheet shape (including a film shape, a ribbon shape, a belt shape), a plate shape, a roll shape, a spherical shape and the like can be mentioned, but the film-forming composition (X) can be easily applied thereon, From the viewpoint that it is easy to irradiate energy rays, it is preferable that the coated surface has a planar shape or a quadric surface shape.

  The substrate may be surface-treated both in the case of resin and in the case of other materials. Surface treatment is for the purpose of preventing dissolution of the substrate by the film-forming composition (X), and for the purpose of improving the wettability of the film-forming composition (X) and improving the adhesion of the super water-repellent film. Etc.

  The surface treatment method of the base material is arbitrary. For example, the polymerizable compound (A) is applied to the surface of the base material and irradiated with energy rays to be cured, corona treatment, plasma treatment, flame treatment, acid or Examples include alkali treatment, sulfonation treatment, fluorination treatment, primer treatment with a silane coupling agent, surface graft polymerization, application of a surfactant or a release agent, physical treatment such as rubbing or sandblasting, and the like. Moreover, the method of reacting with the functional group which a super water-repellent film has, or the functional group introduced by said surface treatment method, and reacting the compound fixed on the surface is mentioned. Among these, when glass or quartz is used as the base material, for example, a method of treating with a silane coupling agent such as trimethoxysilylpropyl (meth) acrylate or triethoxysilylpropyl (meth) acrylate, Since the polymerization group of the silane coupling agent can be copolymerized with the film-forming composition (X), it is useful for improving the adhesion of the super water-repellent film to the substrate.

  The coating method for the film forming composition (X) may be any known method as long as it is a publicly known method. For example, a dipping method, a roll coating method, a doctor blade method, a spin coating method. A coating method such as a coating method or a spray method is preferred.

  Energy rays irradiated in the polymerization process include ultraviolet rays, visible rays, infrared rays, laser rays, radiation rays, etc .; ionizing radiations such as X-rays, gamma rays, radiation rays; electron rays, ion beams, beta rays, heavy particle rays, etc. An example is particle beam. Among these, ultraviolet rays and visible light are preferable from the viewpoint of handleability and curing speed, and ultraviolet rays are particularly preferable. For the purpose of accelerating the curing rate and complete curing, it is preferable to irradiate energy rays in a low oxygen concentration atmosphere. As the low oxygen concentration atmosphere, a nitrogen stream, a carbon dioxide stream, an argon stream, a vacuum or a reduced pressure atmosphere is preferable.

The compound (B) and the polymer (C) produced from the polymerization of the film-forming composition (X) are separated from the polymer polymer (P _A ), the compound (B), and a part of the polymer (C). A method for removing a part of the film can be performed by washing with a solvent. At that time, a region occupied by a part of the compound (B) and the polymer (C) is replaced with a solvent, and then the solvent evaporates in the drying process, thereby forming pores in the film and a concavo-convex structure on the surface. Thus, the production of the super water-repellent film is completed. The solvent can be used without limitation as long as it is compatible with the compound (B) and the polymer (C). However, in order to facilitate the drying operation, it is preferable to use a general-purpose solvent having high volatility such as methanol, ethanol, acetone, hexane, ethyl acetate, diethyl ether and chloroform.

  The super water-repellent membrane produced by the method of the present invention comprises a porous membrane or polymer having an agglomerated particle structure in which particulate polymers having a diameter of about 0.05 μm to 10 μm agglomerate with each other and gaps between the particles become pores. Is a porous film having a three-dimensional network structure in which the particles are aggregated in a network. The obtained super water-repellent film has a thickness of 0.02 to 100 μm and an average surface roughness (Ra) in the range of more than 30 nm to 1000 nm. Moreover, as a super water-repellent film, it is preferable that average surface roughness (Ra) is 40 nm-1000 nm, and it is more preferable that it is 40 nm-500 nm. Within this range, the water contact angle value on the surface is preferably 150 ° or more, which is preferable.

  The average surface roughness (Ra) specified as described above is a value measured by the following equipment (I), and the numerical value of the average surface roughness (Ra) specified in the claims is the equipment (I). It is a measured value.

Instrument (I): Scanning probe microscope (SPI3800N / SPA400): manufactured by SII Nano Technologies Inc. Measurement mode: AFM
Scanning area: 10 μm × 10 μm
Further, data measured by the following apparatus (II) that measures the average surface roughness on the same principle as the above measuring apparatus are also shown as reference values in the section of the following examples.

Equipment (II): Nanoscale hybrid microscope VN-8000: Keyence Corporation Measurement mode: AFM
Scanning area: 10 μm × 10 μm
When measured with the above device (II), the average surface roughness (Ra) of the super water-repellent film obtained by the production method of the present invention is in the range of 20 nm to 1000 nm due to slight differences.

  Moreover, according to the manufacturing method of the present invention, as described above, a highly transparent super water-repellent film can be easily obtained. For example, a transparent super water-repellent film having a visible light transmittance of 80% or more at a wavelength of 600 nm has a film thickness of 0.02 to 1.00 μm and an average surface roughness (Ra) exceeding 30 nm to ˜100 nm. It is characteristic that it is in range. The average surface roughness (Ra) is preferably in the range of 40 nm to 100 nm.

  Moreover, a super water-repellent film excellent in durability can be obtained by repeating the steps of the production method of the present invention. In this case, as the lamination is performed, the pores of the lower layer film are partially filled by the intrusion of the polymer constituting the upper layer film, so that the structure is reinforced and, as a result, the opportunity stability of the film and the surface stability are increased. Abrasion resistance is improved.

EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, this invention is not limited to the range of a following example.
Example 1
(Preparation of substrate)
A glass plate S-1111 (26 mm × 76 mm, thickness 1 mm) manufactured by Matsunami Glass Industry Co., Ltd. was converted into a 5 mmol / L methanol solution of 3- (trimethoxysilyl) propyl methacrylate “M0725” manufactured by Tokyo Chemical Industry Co., Ltd. Was immersed in methanol at 50 ° C. for 3 hours, then ultrasonically washed in methanol, and heated in a constant temperature bath at 100 ° C. under reduced pressure (0.01 Pa or less) for 1 hour to prepare a substrate [S-1].
[Production of super water-repellent film]
Kyoeisha Chemical Co., Ltd. ethylene glycol dimethacrylate “Light Ester EG” 6.94 g, Kyoeisha Chemical Co., Ltd. tert-butyl methacrylate “Light Ester TB” 1.14 g, Kyoeisha Chemical Co., Ltd. perfluorooctylethyl methacrylate “Light Ester FM” 0.18 g of -108 "and 0.18 g of 1-hydroxycyclohexyl phenyl ketone" Irgacure 184 "manufactured by Ciba Geigy as a photopolymerization initiator were uniformly mixed to prepare a polymerizable compound [A-1]. This was uniformly mixed with 4.64 g of methyl decanoate and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich to prepare a film forming composition [X-1].

The film forming composition [X-1] was applied on the substrate [S-1] subjected to the surface treatment using a spin coater under the conditions of 1000 rpm and 10 seconds. Using a UE031-353CHC type UV irradiation device manufactured by Eye Graphics Co., Ltd., which uses a 3000 W metal halide lamp as a light source, the coating film is irradiated with ultraviolet rays having an ultraviolet intensity of 40 mW / cm ² at 365 nm for 3 minutes in a nitrogen stream at room temperature. Then, the film-forming composition [X-1] is polymerized and then washed with ethanol and hexane to form a super-water-repellent film [SH-1] having a thickness of 18 μm formed on the substrate. Obtained.

[Analysis of super water-repellent film]
(1) Water contact angle: 160 ° (falling angle: 1 °)
Measuring device: Kyowa Interface Chemical Automatic Contact Angle Meter DM500
Water droplet volume: 4.0 μl (water droplet photograph is shown in FIG. 1)
(2) Surface morphology: A scanning electron microscope image of the film surface is shown in FIG.
Measuring device: Keyence Real Surface View Microscope VE-9800
Acceleration voltage: 20 kV
(3) Average surface roughness (Ra): 390 nm
Measuring device (Equipment (I)): SII Nano Technologies Scanning Probe Microscope (SPI3800N / SPA400)
Measurement mode: AFM
Scanning area: 10 μm × 10 μm
(4) Reference value Average surface roughness (Ra): 360 nm (atomic force microscope image of film surface is shown in FIG. 3)
Measuring device (equipment (II)): Keyence nanoscale hybrid microscope VN-8000
From the above results, it was confirmed that a super water-repellent polymer film having a fine uneven structure on the surface could be formed on the glass substrate.

(Example 2)
(Preparation of substrate)
Nitto Resin Kogyo Co., Ltd. Methacrylic resin board Clarex S0 (thickness 1 mm) was cut out (53 mm × 80 mm) to obtain a substrate [S-2].
[Production of super water-repellent film]
A super-water-repellent film [SH-2] having a thickness of 19 μm formed on the substrate was prepared in the same manner as in Example 1 except that [S-2] was used instead of [S-1] as the substrate. Obtained.

[Analysis of super water-repellent film]
Water contact angle: 161 ° (Falling angle: 1 °)
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 350 nm
(Equipment (II)) Average surface roughness (Ra): 330 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
From the above results, it was confirmed that a super water-repellent polymer film having a fine concavo-convex structure on the surface could be formed on the methacrylic substrate.

(Example 3)
(Preparation of substrate)
Toyobo Co., Ltd. Biaxially stretched polyester film Cosmo Shine A4300 (thickness 125 μm) was cut out (40 mm × 50 mm) to obtain a substrate [S-3].
[Production of super water-repellent film]
A super-water-repellent film [SH-3] having a thickness of 18 μm formed on the substrate was prepared in the same manner as in Example 1 except that [S-3] was used instead of [S-1]. Obtained.

[Analysis of super water-repellent film]
Water contact angle: 162 ° (Falling angle: 1 °)
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 360 nm
(Equipment (II)) Average surface roughness (Ra): 340 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
From the above results, it was confirmed that a super water-repellent polymer film having a fine uneven structure on the surface could be formed on the polyester base material.

Example 4
[Production of super water-repellent film]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.60 g of methyl octoate and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich to prepare a film forming composition [X-2].
Subsequently, a super water-repellent film having a thickness of 20 μm formed on the substrate in the same manner as in Example 1 except that [X-2] is used instead of the film forming composition [X-1] [ SH-4] was obtained.

[Analysis of super water-repellent film]
Water contact angle: 152 ° (Falling angle: 1 °)
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 310 nm
(Equipment (II)) Average surface roughness (Ra): 300 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
From the above results, it was confirmed that a super water-repellent polymer film having a fine uneven structure on the surface could be formed on the glass substrate.

(Example 5)
[Production of super water-repellent film]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.59 g of ethyl phenylacetate and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich, to prepare a film forming composition [X-3].
Subsequently, a 22 μm-thick super water-repellent film formed on the substrate in the same manner as in Example 1 except that [X-3] was used instead of the film-forming composition [X-1] [ SH-5] was obtained.

[Analysis of super water-repellent film]
Water contact angle: 157 ° (Falling angle: 1 °)
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 330 nm
(Equipment (II)) Average surface roughness (Ra): 320 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
From the above results, it was confirmed that a super water-repellent polymer film having a fine uneven structure on the surface could be formed on the glass substrate.

(Example 6)
[Production of super water-repellent film]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.72 g of tetradecane and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich to prepare a film forming composition [X-4].
Subsequently, a super water-repellent film having a thickness of 21 μm formed on a substrate in the same manner as in Example 1 except that [X-4] is used instead of the film-forming composition [X-1]. SH-6] was obtained.

[Analysis of super water-repellent film]
Water contact angle: 153 ° (fall angle: 1 °)
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 420 nm
(Equipment (II)) Average surface roughness (Ra): 390 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
From the above results, it was confirmed that a super water-repellent polymer film having a fine uneven structure on the surface could be formed on the glass substrate.

(Example 7)
[Production of super water-repellent film]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.65 g of isobutylbenzene and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich to prepare a film forming composition [X-5].
Subsequently, a super water-repellent film having a thickness of 25 μm formed on a substrate in the same manner as in Example 1 except that [X-5] was used instead of the film forming composition [X-1] [ SH-7] was obtained.

[Analysis of super water-repellent film]
Water contact angle: 161 ° (Falling angle: 1 °)
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 370 nm
(Equipment (II)) Average surface roughness (Ra): 350 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
From the above results, it was confirmed that a super water-repellent polymer film having a fine uneven structure on the surface could be formed on the glass substrate.

(Example 8)
[Production of super water-repellent film]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.64 g of diethylene glycol dibutyl ether and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich to prepare a film forming composition [X-6].
Subsequently, a super water-repellent film having a thickness of 20 μm formed on a substrate in the same manner as in Example 1 except that [X-6] is used instead of the film-forming composition [X-1] [ SH-8] was obtained.

[Analysis of super water-repellent film]
Water contact angle: 159 ° (fall angle: 1 °)
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 370 nm
(Equipment (II)) Average surface roughness (Ra): 340 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
From the above results, it was confirmed that a super water-repellent polymer film having a fine uneven structure on the surface could be formed on the glass substrate.

Example 9
[Production of super water-repellent film]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.64 g of methyl decanoate and 0.52 g of polyethyl methacrylate (weight average molecular weight 340,000) manufactured by Aldrich, to prepare a film forming composition [X-7].
Subsequently, a super-water-repellent film having a thickness of 17 μm formed on the substrate in the same manner as in Example 1 except that [X-7] is used instead of the film-forming composition [X-1] [ SH-9] was obtained.

[Analysis of super water-repellent film]
Water contact angle: 155 ° (fall angle: 1 °)
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 310 nm
(Equipment (II)) Average surface roughness (Ra): 300 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
From the above results, it was confirmed that a super water-repellent polymer film having a fine uneven structure on the surface could be formed on the glass substrate.

(Example 10)
[Production of super water-repellent film]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.64 g of methyl decanoate and 0.50 g of polyisobornyl methacrylate (weight average molecular weight 554,000) manufactured by Aldrich to prepare a film forming composition [X-8].
Subsequently, a super water-repellent film having a thickness of 20 μm formed on the substrate in the same manner as in Example 1 except that [X-8] is used instead of the film-forming composition [X-1]. SH-10] was obtained.

[Analysis of super water-repellent film]
Water contact angle: 153 ° (fall angle: 1 °)
Surface morphology: Evaluated using a scanning electron microscope.

(Equipment (I)) Average surface roughness (Ra): 320 nm
(Equipment (II)) Average surface roughness (Ra): 310 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
From the above results, it was confirmed that a super water-repellent polymer film having a fine uneven structure on the surface could be formed on the glass substrate.

(Example 11)
[Production of super water-repellent film]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.64 g of methyl decanoate and 0.48 g of polystyrene (weight average molecular weight 280,000) manufactured by Aldrich to prepare a film forming composition [X-9].
Subsequently, a super water-repellent film having a thickness of 19 μm formed on the substrate in the same manner as in Example 1 except that [X-9] is used instead of the film forming composition [X-1] [ SH-11] was obtained.

[Analysis of super water-repellent film]
Water contact angle: 150 ° (Falling angle: 2 °)
Surface morphology: Evaluated using a scanning electron microscope.

(Equipment (I)) Average surface roughness (Ra): 300 nm
(Equipment (II)) Average surface roughness (Ra): 290 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
From the above results, it was confirmed that a super water-repellent polymer film having a fine uneven structure on the surface could be formed on the glass substrate.

(Example 12)
[Production of super water-repellent film]
Kyoeisha Chemical Co., Ltd. 1,6-hexanediol dimethacrylate “Light Ester 1,6HX” 6.87 g, Kyoeisha Chemical Co., Ltd. n-lauryl methacrylate “Light Ester L” 1.27 g, “Light Ester FM-108” 0.16 g and 0.18 g of “Irgacure 184” as a photopolymerization initiator were uniformly mixed to prepare a polymerizable compound [A-2]. This was uniformly mixed with 4.64 g of methyl decanoate and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich to prepare a film forming composition [X-10].
A super water-repellent film [SH-12] having a thickness of 19 μm formed on a substrate in the same manner as in Example 1 except that [X-10] is used instead of the film-forming composition [X-1]. ] Was obtained.

[Analysis of super water-repellent film]
Water contact angle: 158 ° (Falling angle: 1 °)
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 320 nm
(Equipment (II)) Average surface roughness (Ra): 310 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
From the above results, it was confirmed that a super water-repellent polymer film having a fine uneven structure on the surface could be formed on the glass substrate.

(Example 13)
[Production of super water-repellent film]
Kyoeisha Chemical Co., Ltd. dimethylol tricyclodecane diacrylate “Light acrylate DCP-A” 7.00 g, Osaka Organic Chemical Co., Ltd. isobutyl acrylate “AIB” 1.02 g, Kyoeisha Chemical Co., Ltd. perfluorooctylethyl acrylate “ 0.15 g of light acrylate FA-108 ”and 0.18 g of“ Irgacure 184 ”as a photopolymerization initiator were uniformly mixed to prepare a polymerizable compound [A-3]. This was uniformly mixed with 4.64 g of methyl decanoate and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich to prepare a film forming composition [X-11].
A super water-repellent film [SH-13] having a thickness of 24 μm formed on a substrate in the same manner as in Example 1 except that [X-11] is used instead of the film-forming composition [X-1]. ] Was obtained.

[Analysis of super water-repellent film]
Water contact angle: 156 ° (Falling angle: 1 °)
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 410 nm
(Equipment (II)) Average surface roughness (Ra): 390 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
From the above results, it was confirmed that a super water-repellent polymer film having a fine uneven structure on the surface could be formed on the glass substrate.

(Example 14)
[Production of super water-repellent film]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.72 g of methyl tetradecanoate and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich, to prepare a film forming composition [X-12].
The film-forming composition [X-12] was coated on the substrate [S-1] that had been surface-treated by the same method as in Example 1 using a spin coater under the conditions of 4000 rpm and 25 seconds. . The coating film is polymerized in the same manner as in Example 1, followed by washing to obtain a 1.0 μm-thick super water-repellent film [SH-14] formed on the substrate. It was.

[Analysis of super water-repellent film]
Water contact angle: 155 ° (falling angle: 1 °) (Water droplet photograph is shown in FIG. 4)
Surface morphology: A scanning electron microscope image of the film surface is shown in FIG.
(Equipment (I)) Average surface roughness (Ra): 52 nm (Atomic force microscope image of film surface is shown in FIG. 16)
(Equipment (II)) Average surface roughness (Ra): 43 nm (Atomic force microscope image of film surface is shown in FIG. 6)
The measurement apparatus, measurement conditions, and the like are as described in Example 1.
Visible light transmittance: 92.0% (wavelength 540 nm), 95.3% (wavelength 600 nm)
Measuring apparatus: Hitachi UV-visible spectrophotometer U-4100
From the above results, it was confirmed that a super-water-repellent polymer film having a fine concavo-convex structure on the surface and excellent in transparency could be formed on the glass substrate.

(Example 15)
[Production of super water-repellent film]
A polymerizable compound [A-3] was prepared in the same manner as in Example 13. This was uniformly mixed with 4.75 g of methyl hexadecanoate and 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich to prepare a film forming composition [X-13].

  The film-forming composition [X-13] was applied on the substrate [S-1] that had been surface-treated by the same method as in Example 1 using a spin coater under the conditions of 7000 rpm and 25 seconds. . The coating film is polymerized in the same manner as in Example 1, followed by washing to obtain a super-water-repellent film [SH-15] having a thickness of 0.7 μm formed on the substrate. It was.

[Analysis of super water-repellent film]
Water contact angle: 154 ° (Falling angle: 1 °)
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 50 nm
(Equipment (II)) Average surface roughness (Ra): 35 nm
Visible light transmittance: 95.4% (wavelength 540 nm), 98.0% (wavelength 600 nm)
The measurement apparatus, measurement conditions, etc. are as described in Example 1 and Example 14.
From the above results, it was confirmed that a super-water-repellent polymer film having a fine concavo-convex structure on the surface and excellent in transparency could be formed on the glass substrate.

(Example 16)
[Production of super water-repellent film]
A film-forming composition [X-1] was prepared in the same manner as in Example 1. This was uniformly mixed with 50.5 g of ethyl acetate to prepare a film forming composition [X-14].
The film forming composition [X-14] was applied on the substrate [S-1] that had been surface-treated by the same method as in Example 1 using a spin coater under the conditions of 2000 rpm and 180 seconds. . The coating film is polymerized in the same manner as in Example 1, followed by washing to obtain a 0.5 μm-thick super water-repellent film [SH-16] formed on the substrate. It was.

[Analysis of super water-repellent film]
Water contact angle: 151 ° (falling angle: 2 °) (Water droplet photograph is shown in FIG. 7)
Surface morphology: A scanning electron microscope image of the film surface is shown in FIG.

(Equipment (I)) Average surface roughness (Ra): 46 nm (Atomic force microscope image of film surface is shown in FIG. 19)
(Equipment (II)) Average surface roughness (Ra): 30 nm (Atomic force microscope image of film surface is shown in FIG. 9)
Visible light transmittance: 95.9% (wavelength 540 nm), 98.0% (wavelength 600 nm)
The measurement apparatus, measurement conditions, etc. are as described in Example 1 and Example 14.
From the above results, it was confirmed that a super-water-repellent polymer film having a fine concavo-convex structure on the surface and excellent in transparency could be formed on the glass substrate.

(Example 17)
[Production of super water-repellent film]
A film-forming composition [X-1] was prepared in the same manner as in Example 1. This was uniformly mixed with 9.23 g of hexane to prepare a film-forming composition [X-15].
The film-forming composition [X-15] was applied on the substrate [S-1] that had been surface-treated by the same method as in Example 1 using a spin coater under the conditions of 2000 rpm and 180 seconds. . The coating film is polymerized in the same manner as in Example 1, followed by washing to obtain a 0.6 μm-thick super water-repellent film [SH-17] formed on the substrate. It was.

[Analysis of super water-repellent film]
Water contact angle: 150 ° (Falling angle: 2 °)
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 53 nm
(Equipment (II)) Average surface roughness (Ra): 38 nm
Visible light transmittance: 95.9% (wavelength 540 nm), 99.2% (wavelength 600 nm)
The measurement apparatus, measurement conditions, etc. are as described in Example 1 and Example 14.

  From the above results, it was confirmed that a super-water-repellent polymer film having a fine concavo-convex structure on the surface and excellent in transparency could be formed on the glass substrate.

(Example 18)
[Production of super water-repellent film]
A film-forming composition [X-1] was prepared in the same manner as in Example 1. This was uniformly mixed with 9.25 g of toluene to prepare a film forming composition [X-16].
The film-forming composition [X-16] was applied on the substrate [S-1] that had been surface-treated by the same method as in Example 1 using a spin coater under the conditions of 2000 rpm and 180 seconds. . The coating film is polymerized in the same manner as in Example 1, followed by washing to obtain a 0.5 μm thick super water-repellent film [SH-18] formed on the substrate. It was.

[Analysis of super water-repellent film]
Water contact angle: 152 ° (Tumble angle: 2 °)
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 51 nm
(Equipment (II)) Average surface roughness (Ra): 33 nm
Visible light transmittance: 98.1% (wavelength 540 nm), 99.0% (wavelength 600 nm)
The measurement apparatus, measurement conditions, etc. are as described in Example 1 and Example 14.
From the above results, it was confirmed that a super-water-repellent polymer film having a fine concavo-convex structure on the surface and excellent in transparency could be formed on the glass substrate.

(Example 19)
[Production of super water-repellent film]
A film-forming composition [X-1] was prepared in the same manner as in Example 1. This was uniformly mixed with 50.4 g of chloroform to prepare a film forming composition [X-17].
The film forming composition [X-17] was coated on the substrate [S-1] that had been surface-treated by the same method as in Example 1 using a spin coater under the conditions of 2000 rpm and 180 seconds. . The coating film is polymerized in the same manner as in Example 1, and then washed to obtain a 0.6 μm-thick super water-repellent film [SH-19] formed on the substrate. It was.

[Analysis of super water-repellent film]
Water contact angle: 151 ° (fall angle: 2 °)
Surface morphology: Evaluated using a scanning electron microscope.

(Equipment (I)) Average surface roughness (Ra): 43 nm
(Equipment (II)) Average surface roughness (Ra): 28 nm
Visible light transmittance: 96.1% (wavelength 540 nm), 98.7% (wavelength 600 nm)
The measurement apparatus, measurement conditions, etc. are as described in Example 1 and Example 14.
From the above results, it was confirmed that a super-water-repellent polymer film having a fine concavo-convex structure on the surface and excellent in transparency could be formed on the glass substrate.

(Comparative Example 1)
[Preparation of energy-ray cured film]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 4.65 g of methyl hexanoate to prepare a film forming composition [XR-1].
Subsequently, an energy ray cured film having a thickness of 14 μm formed on a substrate in the same manner as in Example 1 except that [XR-1] is used instead of the film-forming composition [X-1]. R-1] was obtained.

[Analysis of energy ray cured film]
Water contact angle: 65 °
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 3.2 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
Thus, the energy ray cured film prepared using the film-forming composition containing methyl hexanoate having a saturated vapor pressure at 25 ° C. of 670 Pa as the compound (B) did not exhibit super water repellency.

(Comparative Example 2)
[Preparation of energy-ray cured film]
In the same manner as in Example 11, polymerizable compound [A-2] was prepared. This was uniformly mixed with 4.65 g of methyl hexanoate to prepare a film forming composition [XR-2].
Subsequently, an energy ray cured film having a thickness of 16 μm formed on a substrate in the same manner as in Example 1 except that [XR-2] is used instead of the film-forming composition [X-1]. R-2] was obtained.

[Analysis of energy ray cured film]
Water contact angle: 68 °
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 2.5 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
Thus, the energy ray cured film prepared using the film-forming composition containing methyl hexanoate having a saturated vapor pressure at 25 ° C. of 670 Pa as the compound (B) did not exhibit super water repellency.

(Comparative Example 3)
[Preparation of energy-ray cured film]
In the same manner as in Example 12, polymerizable compound [A-3] was prepared. This was uniformly mixed with 4.65 g of methyl hexanoate to prepare a film forming composition [XR-3].
Subsequently, an energy ray cured film having a thickness of 14 μm formed on the substrate in the same manner as in Example 1 except that [XR-3] is used instead of the film-forming composition [X-1]. R-3] was obtained.

[Analysis of energy ray cured film]
Water contact angle: 65 °
(Equipment (I)) Average surface roughness (Ra): 1.9 nm
Surface morphology: Evaluated using a scanning electron microscope.
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
Thus, the energy ray cured film prepared using the film-forming composition containing methyl hexanoate having a saturated vapor pressure at 25 ° C. of 670 Pa as the compound (B) did not exhibit super water repellency.

(Comparative Example 4)
[Preparation of energy-ray cured film]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 0.52 g of polyisobutyl methacrylate (weight average molecular weight 300,000) manufactured by Aldrich to prepare a film forming composition [XR-4].
Subsequently, an energy ray cured film having a thickness of 19 μm formed on a substrate in the same manner as in Example 1 except that [XR-4] is used instead of the film forming composition [X-1] [ R-4] was obtained.

[Analysis of energy ray cured film]
Water contact angle: 108 °
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 17 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
Thus, the energy ray cured film prepared using the film-forming composition containing no compound (B) did not exhibit super water repellency.

(Comparative Example 5)
[Preparation of energy-ray cured film]
In the same manner as in Example 1, polymerizable compound [A-1] was prepared. This was uniformly mixed with 0.52 g of polyethyl methacrylate (weight average molecular weight 340,000) manufactured by Aldrich to prepare a film forming composition [XR-5].
Subsequently, an energy ray cured film having a thickness of 17 μm formed on a substrate in the same manner as in Example 1 except that [XR-5] is used instead of the film-forming composition [X-1]. R-5] was obtained.

[Analysis of energy ray cured film]
Water contact angle: 98 °
Surface morphology: Evaluated using a scanning electron microscope.

(Equipment (I)) Average surface roughness (Ra): 20 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.
Thus, the energy ray cured film prepared using the film-forming composition containing no compound (B) did not exhibit super water repellency.

(Comparative Example 6)
[Preparation of energy-ray cured film]
A polymerizable compound [A-3] was prepared in the same manner as in Example 13. This was uniformly mixed with 0.48 g of polystyrene (weight average molecular weight 280,000) manufactured by Aldrich to prepare a film forming composition [XR-6].
Subsequently, an energy ray cured film having a thickness of 14 μm formed on a substrate in the same manner as in Example 1 except that [XR-6] is used instead of the film forming composition [X-1]. R-6] was obtained.

[Analysis of energy ray cured film]
Water contact angle: 78 °
Surface morphology: Evaluated using a scanning electron microscope.
(Equipment (I)) Average surface roughness (Ra): 15 nm
The measurement apparatus, measurement conditions, etc. are as described in Example 1.

  Thus, the energy ray cured film prepared using the film-forming composition containing no compound (B) did not exhibit super water repellency.

Claims (12)

A polymerizable compound (A) polymerizable by irradiation with energy rays;
A compound (B) that is compatible with the polymerizable compound (A) but is not compatible with the polymer polymer (P _A ) of the polymerizable compound ( _A ) and is inactive with respect to energy rays. ,
A step of producing a film-forming composition (X) in which the polymerizable compound (A) and the compound (B) are compatible with each other and a polymer (C) that is inert to energy rays is mixed;
Forming a layer of the film-forming composition (X);
A method for producing a water-repellent film comprising the step of polymerizing the polymerizable compound (A) in the film-forming composition (X) by irradiation with energy rays and then removing the compound (B).   The method for producing a water-repellent film according to claim 1, wherein the compound (B) is a compound (D) having a liquid or solid state, a molecular weight of 500 or less, and a saturated vapor pressure at 25 ° C of 600 Pa or less.   The method for producing a water-repellent film according to claim 1, wherein the compound (B) is the compound (D) and a liquid compound (E) having a saturated vapor pressure at 25 ° C of 600 Pa or more. The compound (D) is selected from the group consisting of compounds represented by the formula (1), formula (2), formula (3) and formula (4), and optionally branched alkanes having 10 to 20 carbon atoms. The method for producing a water-repellent film according to claim 2, wherein the water-repellent film is one or more selected compounds.

(In the formula (1), R ₁ represents an alkyl group or benzyl group having 7 to 19 carbon atoms, and R ₂ represents a methyl group or an ethyl group.)

(In Formula (2), R ₃ represents a methyl group or an ethyl group, and R ₄ represents an alkyl group having 8 to 20 carbon atoms which may be branched or a benzyl group.)

(In formula (3), R _{5 to} R ₁₀ each independently represents a hydrogen atom or an optionally branched alkyl group, and at least two of them are ethyl groups, or at least one of them has 3 carbon atoms. It is the alkyl group which may be branched of -8.

(In Formula (4), R ₁₁ and R ₁₂ each independently represents an alkyl group having 2 to 8 carbon atoms which may be branched.) The compound (E) is, pentane, hexane, _heptane, R 13 COOR ₁₄ (wherein _{R 13} and _{R 14} is each independently represent an alkyl group having 1 to 5 carbon _atoms, the carbon of _{R 13} and _{R 14} The total number is 6 or less.), R ₁₅ COR ₁₆ (wherein R ₁₅ and R ₁₆ each independently represents an alkyl group having 1 to 5 carbon atoms, but the number of carbon atoms of R ₁₅ and R ₁₆ is The total is 6 or less.), R ₁₇ OR ₁₈ (wherein R ₁₇ and R ₁₈ each independently represents an alkyl group having 1 to 6 carbon atoms, but the total number of carbon atoms of R ₁₇ and R ₁₈ is The method for producing a water-repellent film according to claim 3, which is at least one compound selected from the group consisting of benzene, toluene, dichloromethane, chloroform, and carbon tetrachloride. The method for producing a water-repellent film according to any one of claims 1 to 5, wherein the polymer (C) is an acrylic copolymer or a styrene copolymer.   The method for producing a water-repellent film according to any one of claims 1 to 6, wherein the polymer (C) has a molecular weight in the range of 10,000 to 1,000,000.   The method for producing a water-repellent film according to any one of claims 1 to 8, wherein a super-water-repellent film having a contact angle with water on the film surface of 150 ° or more is produced.   A water repellent film obtained by the method according to claim 1. The water repellent film according to claim 9, wherein an average surface roughness (Ra) of the water repellent film is in a range of more than 30 nm and up to 1000 nm. The water repellent film according to claim 9 or 10, wherein the transmittance of visible light having a wavelength of 600 nm is 80% or more.   A polymer of a polymerizable compound (A) that can be polymerized by irradiation with energy rays, and a polymer (C) that is compatible with the polymerizable compound (A) and inert to energy rays, and has an average A water-repellent film having a surface roughness (Ra) in the range of more than 30 nm to 1000 nm.

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