JP2006144029A - Resin board having hydrophilic or water-repellent film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin board having hydrophilic or water-repellent film that can be formed with high hardness even on the surface of a resin having low heat resistance. <P>SOLUTION: The hydrophilic film is formed on a resin and is formed of an inorganic oxide. The hydrophilic film has voids with a size in the range of 20-200 nm. The hydrophilic film with high hardness and increased abrasion resistance compared with hydrophilic films without voids can be obtained. Too large rate of voids must be avoided since it decreases the strength of the film. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hydrophilic film and a water-repellent film formed on a resin.

  Attempts have been made to make the resin surface hydrophilic for easy removal of dirt, anti-fogging, improvement of paint wettability, adhesion and adhesion.

  As conventional techniques, a method of forming a coating film containing titanium oxide particles (see, for example, Patent Document 1) and a method of forming a coating film including a hydrophilic material such as colloidal silica (see, for example, Patent Document 2) are disclosed. Has been.

  In general, thermal curing is used for curing these coating films. This is because a material as a binder such as silica sol or acrylamide is polymerized by heating to exhibit a function as a binder.

International Publication No. 96/29375 Pamphlet JP-A-8-80474

  In the case of the above-mentioned silica sol, the heating temperature is ideally 300 to 500 ° C., but a coating film having a pencil hardness of about 2H can be formed even at about 160 ° C.

  However, in the case of a resin such as thermoplastic acrylic or polycarbonate, the shape is deformed when the heating temperature is 100 ° C. or higher or 120 ° C. or higher, respectively. Therefore, it is necessary to lower the heat effect temperature, but if it is too low, only a coating film with extremely low hardness can be formed.

  On the other hand, a method of coating the resin surface with a fluorine-containing compound to make the resin surface water-repellent to prevent dirt adhesion, water droplet adhesion, etc. has been studied. A fluorine-containing compound having an alkoxysilane residue is effective.

  However, since the alkoxysilane residue reacts with the hydroxyl group on the surface to form a chemical bond, in the case of a resin such as acrylic or polycarbonate that does not have a hydroxyl group on the resin surface, a silicon oxide film using silica sol as a raw material is formed on the resin. A method is effective in which a fluorine-containing compound having an alkoxysilane residue at the terminal is applied and then heated to form a chemical bond with a hydroxyl group on the silicon oxide surface. Also in this case, only the water-repellent film having low hardness can be formed because the thermosetting temperature when forming the silicon oxide film is low.

  As described above, an object of the present invention is to form a high-hardness hydrophilic film or water-repellent film on the surface of a resin having a low heat-resistant temperature.

  As a means for achieving the above object, in the present invention, a resin plate having a hydrophilic film, the hydrophilic film is formed on the resin plate, and a water repellent film is formed on the hydrophilic film, The hydrophilic film has a void having a size of 20 nm or more and 200 nm or less, and the water-repellent film is formed by including a material having the following structure.

  Also, a resin plate having a hydrophilic film, wherein the hydrophilic film is formed on the resin plate, a water-repellent film is formed on the hydrophilic film, and the hydrophilic film has a gap of 20 nm to 200 nm in size. And the water-repellent film is formed by including a material having the following structure.

  Further, the resin film is characterized in that the hydrophilic film is formed of silicon oxide, and the volume ratio of the voids is 2% or more and 14% or less of the entire volume of the hydrophilic film. Take the board configuration.

  Further, the hydrophilic film is formed on the resin plate by applying a liquid in which at least silica sol and colloidal silica are mixed.

  As described above, a highly rigid hydrophilic film or water-repellent film can be formed on the surface of a resin having a low heat-resistant temperature.

  First, the outline of the present invention will be described. However, the present invention is not limited to specific examples as long as the gist of the invention is not exceeded.

  FIG. 1 is a cross-sectional photograph of a resin according to the present invention, in which a hydrophilic film is provided on the resin. The resin described in FIG. 1 is an acrylic resin plate, and a hydrophilic film is formed on the resin, and carbon is further formed on the hydrophilic film. Here, carbon is formed only for preparing a sample of a cross section in the measurement, and even if it does not exist, the effect of the present invention is exhibited.

  Further, the hydrophilic film thickness is about 200 nm, and it can be seen that there is an island-like region near the hydrophilic film surface. Therefore, the existence strength of the element in each of the island-like region and the region other than the island-like region was measured. The result is shown in FIG.

  As a result of FIG. 2, it can be seen that the existence intensity of carbon, oxygen, silicon, and the like in the island-shaped region is clearly smaller than the regions other than the island-shaped region. That is, it can be determined that the island-shaped region is a void and the region other than the island-shaped region is a hydrophilic film. A hydrophilic film having such voids has a higher hardness than a hydrophilic film without voids, and is considered to play a role of improving abrasion resistance. However, it should be noted that if the void ratio is too large, the strength of the film is reduced.

  The resin having a hydrophilic film including voids can be formed by applying a paint (hydrophilic paint) for forming a hydrophilic film on the resin plate and quickly heating the resin plate and the coating film. This is thought to be due to the fact that the surface near the surface of the coating was rapidly cured by heating, but when the solvent derived from the paint inside the coating was subsequently volatilized, the cured coating near the surface could not be transmitted and voids were formed. . Therefore, a desired hydrophilic film can be formed by appropriately performing the treatment before coating the coating and the curing conditions after coating.

  The water-repellent film according to the present invention can be produced by forming a monomolecular layer made of a fluorine-containing compound on the hydrophilic film. Since the fluorine-containing compound is a monomolecular layer, the strength of the film is determined by the underlying hydrophilic film. Further, since the water-repellent film itself has lubricity, the abrasion resistance is improved, and the pencil hardness tends to be improved as compared with the hydrophilic film.

  Embodiments of the present invention will be described below.

[1] Hydrophilic film (1) Method for forming hydrophilic film The hydrophilic film according to the present invention is obtained by applying a paint (hydrophilic paint) for forming a hydrophilic film on a resin, and heating and heating the hydrophilic coating film. Can be formed. Details will be described below.

First, the wettability of the resin surface is improved by irradiating the resin with ultraviolet light, oxygen plasma irradiation, leaving it in an oxygen plasma atmosphere, or leaving it in an ozone atmosphere. Ultraviolet light irradiation can be performed with a high-pressure mercury lamp or an ultra-high pressure mercury lamp, but a lamp that irradiates ultraviolet light, such as DeepUV lamp and low-pressure mercury lamp, which easily generates ozone such as 254 nm is effective. In addition, when the resin is a flat plate, it is effective to perform irradiation with ultraviolet light or oxygen plasma, and when there are many uneven structures, it is effective to leave the resin in an oxygen plasma atmosphere or an ozone atmosphere. In this process, when the resin is an acrylic resin, conditions are set so that the contact angle with water, which is around 95 ° before the process, is 50 ° or less after the process. In the case of polycarbonate, PMMA, etc., conditions are set so as to be 50 ° or less after the treatment. In the case of hydrocarbon resins such as polyethylene and polypropylene, conditions need to be tighter than acrylic, but the contact angle with water that is around 80 to 90 ° before treatment should be 70 degrees or less after treatment. Set conditions.

  When ultraviolet rays are irradiated, it is possible to drastically improve the hardness of the hydrophilic film formed after the application of the hydrophilic paint and thermal curing by using heating of the resin plate in combination. The heating temperature may be set in the vicinity of the heat deformation temperature of the resin (specifically, the heat deformation temperature ± 20 ° C.). For example, in the case of a resin having a heat deformation temperature of 100 ° C., the temperature is set to 80 ° C. to 120 ° C., and in the case of a resin having a heat deformation temperature of 110 ° C., 90 ° C. to 130 ° C. As a result, when the operation is not performed, only a hydrophilic film having a pencil hardness of 2B or less can be formed. By performing this operation, a hydrophilic film having a hardness of several H can be formed. The thermal deformation temperature described in this specification is defined as a temperature at which a plate (length × width × thickness = 100 mm × 100 mm × 5 mm) formed into a predetermined size generates warpage upon heating. In addition, the heating time in that case is 30 minutes. That is, even when the heating temperature is higher than the thermal deformation temperature, the processing can be performed without causing deformation by shortening the heating time.

  Next, a hydrophilic paint is applied. As a coating method, a normal coating method such as dip coating, spin coating, spray coating, or coating with a bar coater can be used.

  Finally heat. This temperature needs to be lower than the heat distortion temperature of the resin. In curing, the surface of the coating film is rapidly heated at the curing temperature. This facilitates the formation of voids in the hydrophilic film.

(2) Hydrophilic paint The hydrophilic paint comprises a hydrophilic material, a holding material for holding the hydrophilic material, and a solvent.

(A) Hydrophilic material Examples of the hydrophilic material include organic polymer materials such as polyethylene glycol and polyvinyl alcohol, and inorganic materials such as hydrophilic alumina particles and hydrophilic silica particles. Among these, inorganic materials such as hydrophilic alumina particles and hydrophilic silica particles are superior in that those that do not dissolve even when immersed in water for a long period of time can maintain a long hydrophilicity (these inorganic materials are inorganic oxides). Become). In addition, these inorganic fine particles are often dispersed in water. In this case, the water content increases as a paint, so the water content increases when it is applied to the substrate surface and then dried, resulting in the substrate surface There is a possibility of being played. This is because the surface tension of water is 72 mN / m, which is larger than that of general-purpose organic solvents. For this reason, it is better to use a solvent having a small surface tension of 20 to 30 mN / m, such as alcohol and ethyl methyl ketone, than water. As the hydrophilic material used in the present invention, hydrophilic silica particles are particularly preferable in that they can be dispersed in an organic solvent such as alcohol ethyl methyl ketone. Specific examples include colloidal silica IPA-ST and MEK-ST manufactured by Nissan Chemical.

(B) Retainer material The retainer material is an organic polymer material such as polyethylene glycol or polyvinyl alcohol, an organic material that is polymerized by heating, such as acrylamide, or an inorganic retainer, by heating, such as silica sol. Materials and the like. Among these, materials such as acrylamide and silica sol are superior in that those that do not dissolve even when immersed in water for a long period of time can maintain a long hydrophilicity. In addition, there is compatibility when holding the hydrophilic material, and silica sol is particularly suitable for the inorganic hydrophilic material.

  Silica sol is a product of self-polymerization of molecular weight of several thousand by heating alkoxysilane in water acidified with dilute hydrochloric acid, dilute nitric acid, or dilute phosphoric acid, or in a water-alcohol mixture. Examples of the alkoxysilane include methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, tetramethoxysilane, and tetraethoxysilane. Note that alkoxy titanium may be used instead of alkoxy silane as long as the liquidity and the solvent match. Examples of the alkoxytitanium include tetra-i-propyl titanate, tetra-n-butyl titanate, tetrastearyl titanate, triethanolamine titanate, titanium acetylacetonate, titanium ethyl acetoacetate, titanium lactate, and tetraoctylene glycol titanate. Further, those obtained by polymerizing several compounds of these compounds can also be used.

  By the way, even if an alkoxysilane having an amino group is used instead of the silica sol, the same holding performance as that of the silica sol can be exhibited. In addition, when exposed to an acidic gas atmosphere, the amino group changes to an ammonium salt structure, and as a result, the hydrophilicity of the film can be further improved. As such a material, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (trade name is, for example, Silaace S310 manufactured by Chisso Corporation), 3-aminopropyltriethoxysilane (trade name is, for example, CHISSO Co., Ltd. Silaace S330), 3-aminopropyltrimethoxysilane (trade names include, for example, Chisso Corporation Silaace S360), and the like. Further, examples include Silaace oligomer MS3201 and MS3301 manufactured by Chisso Corporation, which are compounds obtained by polymerizing several molecules such as S320 and S330.

(C) Solvent The solvent has good compatibility (dispersibility and compatibility) with the hydrophilic material and the support material, and it is desirable that the solvent volatilizes easily during thermosetting. In particular, in order to form voids in the hydrophilic film, it is desirable that the boiling point of the solvent is lower than the thermosetting temperature. Among the hydrophilic materials, alcohol-based solvents are preferable in that hydrophilic alumina particles and hydrophilic silica particles, which are highly durable and preferable materials, are well dispersed. Alcohol solvents are also preferred because they are highly compatible with silica sols that are suitable as support materials. Considering the heat resistance of the resin, the thermosetting temperature is 100 ° C. or lower for acrylic and 120 ° C. or lower for polycarbonate. Examples of alcohols having a boiling point of 100 ° C. or lower include methanol, ethanol, n-propanol, and isopropanol. When a solvent such as n-butanol having a higher boiling point than n-propanol is used, the porosity tends to be too large and the hardness tends to decrease. In order to make the pencil hardness of the hydrophilic film 2H or more, the porosity is desirably 2 to 14% in terms of volume ratio with respect to the hydrophilic film.

(D) Lubricant There is also a method of improving the lubricity of the surface and consequently improving the abrasion resistance. Lubricating property is improved by adding about 0.01 to 0.5% by weight of a solid lubricant, and as a result, abrasion resistance is also improved. However, if 2% or more of the solid content is added, the hydrophilicity of the surface tends to decrease. The silicone-based lubricant is desirably dissolved in the solvent of the coating material used for producing the hydrophilic film, but it is also possible to use a silicone lubricant that is substantially uniformly dispersed for a certain period of time if it is not dissolved. Specific examples thereof include BYK-370 and BYK- manufactured by BYK-Chemie.
310 etc. are mentioned.

[2] Water-repellent film The water-repellent film according to the present invention is formed of the following fluorine-containing compound.

Since these compounds have alkoxysilane residues at their ends, the surface that can be treated is glass, metal, or the surface of a resin having a hydroxyl group. Therefore, when forming on the resin surface, it is necessary to deposit a metal on the resin surface in advance or form a SiO ₂ film with silica sol or the like. Since the surface of the hydrophilic film of the present invention has more hydroxyl groups for exerting hydrophilicity than ordinary glass or metal, it is preferable because the power factor of the fluorine-containing compound is improved and the water repellency is increased. Therefore, the method for forming the water-repellent film of the present invention will be described as a method of forming on the hydrophilic film of the present invention.

(1) Method for forming water-repellent film The water-repellent film of the present invention is formed by applying a paint containing the above-mentioned fluorine-containing compound (hereinafter referred to as a water-repellent paint) and then heating it. Heating is a condition necessary for the alkoxysilane residue to form a Si—O bond with the surface, and is usually about 10 minutes at 120 ° C., 30 minutes at 100 ° C., and about 1 hour at 90 ° C. Although it proceeds at room temperature, it takes a considerable amount of time.

(2) Water-repellent paint The paint used to form the water-repellent film of the present invention is obtained by dissolving 0.01 to 0.5% by weight of the fluorine-containing compound in a fluorine-based solvent. The concentration is set higher for the fluorine-containing compound having a larger average molecular weight. When the average molecular weight is around 3000, the concentration is preferably about 0.03 to 0.3% by weight.

  The water-repellent paint is applied by brush coating, dip coating, spin coating or the like.

(A) Fluorine-containing compound Specific examples of the fluorine-containing compound include the following compounds 1 to 12.

Among these, the compounds 1-8 are obtained by performing the synthesis method shown below. Compound 9 ~
12 are compound names 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane, 1H,
1H, 2H, 2H-perfluorodecyltrimethoxysilane and 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane are marketed by Hydras Chemical. Another commercially available material is Daikin Industries, Ltd. OPTOOL DSX. Compounds 1-4 are those whose fluorine chains are called perfluoropolyether, and the water-repellent film formed from this compound having fluorine chains is immersed in engine oil, gasoline, etc. for a long time (1000 hours) in addition to water. However, the water repellency hardly decreases (the amount of decrease is 5 ° or less). These compounds are represented by the following general formula.

  When the compounds 5 to 12 are immersed in engine oil or gasoline for a long period (1000 hours), the contact angle with water decreases from before the immersion (about 110 ° C.) to almost the same level as the contact angle of the substrate.

(Synthesis of Compound 1)
DuPont Krytox 157FS-L (average molecular weight 2500) (25 parts by weight) was dissolved in 3M PF-5080 (100 parts by weight), thionyl chloride (20 parts by weight) was added thereto, and the mixture was stirred for 48. Reflux for hours. Thionyl chloride and PF-5080 are volatilized with an evaporator to obtain acid chloride (25 parts by weight) of Krytox 157FS-L. PF-5080 (100 parts by weight), Silaace S330 (3 parts by weight) manufactured by Chisso Corporation, and triethylamine (3 parts by weight) are added to this and stirred at room temperature for 20 hours. The reaction solution was filtered with Radiolight Fine Flow A manufactured by Showa Chemical Industry, and PF-5080 in the filtrate was volatilized with an evaporator to obtain Compound 1 (20 parts by weight).

(Synthesis of Compound 2)
Compound 2 (20 parts by weight) was obtained in the same manner as in the synthesis of Compound 1 except that Chisso Co., Ltd. Silaace S330 (3 parts by weight) was used instead of Chisso Co., Ltd. Silaace S360 (3 parts by weight).

(Synthesis of Compound 3)
Compound similar to the synthesis of Compound 1 except that Daikin Industries' demnum SH (average molecular weight 3500) (35 parts by weight) is used instead of DuPont Krytox 157FS-L (average molecular weight 2500) (25 parts by weight) 3 (30 parts by weight) was obtained.

(Synthesis of Compound 4)
Instead of Chisso Corporation Silaace S330 (3 parts by weight), Chisso Corporation Silaace S360 was used, and DuPont's Krytox 157FS-L (average molecular weight 2500) (25 parts by weight) was made by Daikin Industries, Ltd. Compound 4 (30 parts by weight) was obtained in the same manner as in the synthesis of Compound 1, except that demnam SH (average molecular weight 3500) (35 parts by weight) was used.

(Synthesis of Compound 5)
Compound 1 except that 7H-dodecafluoroheptanoic acid (molecular weight 346.06) (3.5 parts by weight) manufactured by Daikin Industries, Ltd. was used instead of DuPont's Krytox 157FS-L (average molecular weight 2500) (25 parts by weight) In the same manner as in the synthesis of Compound 5 (3.5 parts by weight) was obtained.

(Synthesis of Compound 6)
Chisso Co., Ltd. was used instead of DuPont's Krytox 157FS-L (average molecular weight 2500) (25 parts by weight) 7K-dodecafluoroheptanoic acid (molecular weight 346.006) (3.5 parts by weight) manufactured by Daikin Industries, Ltd. ) Compound 6 (3.5 parts by weight) was obtained in the same manner as in the synthesis of Compound 1, except that Chisso Corporation Silaace S320 (2 parts by weight) was used instead of Silaace S310 (2 parts by weight).

(Synthesis of Compound 7)
Daikin Industries, Ltd. 9H-hexadecafluorononanoic acid (molecular weight 446.07) instead of DuPont's Krytox 157FS-L (average molecular weight 2500) (25 parts by weight)
Compound 7 (4.5 parts by weight) was obtained in the same manner as in the synthesis of Compound 1 except that (4.5 parts by weight) was used.

(Synthesis of Compound 8)
Daikin Industries, Ltd. 9H-hexadecafluorononansan (molecular weight 446.07) instead of DuPont Krytox 157FS-L (average molecular weight 200) (25 parts by weight)
(4.5 parts by weight) and the same method as in the synthesis of Compound 1 except that Chisso Corp. Silaace S310 (2 parts by weight) is used instead of Chisso Corp. Silaace S310 (2 parts by weight). 8 (4.5 parts by weight) was obtained.

(B) Solvent Specific examples of the fluorine-based solvent for dissolving the above-mentioned fluorine-containing compound include 3M FC-72, FC-77, PF-5060, PF-5080, HFE7100, HFE7200, and DuPont Vertrel XF. It is done.

[3] Applications As applications of the resin having the hydrophilic film and the water-repellent film of the present invention, there can be considered vehicle windows for automobiles and trucks, windows for houses and buildings, and the like. Because it is lighter than conventional glass and has a high degree of freedom in shape, it can be fitted with windows that are difficult to design with glass. Moreover, since it is hard to break, it is also effective in terms of safety.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

  First, a method for creating a hydrophilic film on an acrylic plate will be described.

(1) Pretreatment of applying hydrophilic paint After placing a transparent acrylic plate (manufactured by AS ONE) 100mm long, 100mm wide and 5mm thick on a hot plate heated to 90 ° C, quickly irradiate ultraviolet light with a low-pressure mercury lamp. Irradiated. The amount of irradiation light is 10 mW, and the irradiation time is 5 minutes (the time for heating to 90 ° C. is also 5 minutes). Thereby, the contact angle with the water of the acrylic board surface which received ultraviolet light irradiation became 30 degrees or less. In addition, the contact angle with the water of the acrylic board surface before ultraviolet light irradiation was 90-95 degrees. Moreover, the heat deformation temperature of the used acrylic board was 100 degreeC.

(2) Hydrophilic treatment Silica sol solution (acidic phosphate, solvent is water: ethanol = 2: 8, fixed sentence is 6% by weight)
(1 part by weight), colloidal silica composed of silicon oxide (Nissan Chemical IPA-ST, solid content is 30% by weight) (2 parts by weight), and ethanol (15 parts by weight) are mixed to adjust the hydrophilic coating. .

  This paint is applied by spin coating to the acrylic plate which has been irradiated with ultraviolet light. The spin coating conditions are a rotation speed of 1200 rpm and a rotation time of 25 seconds. The applied paint spread almost uniformly in an acrylic plate shape by visual observation.

(3) Thermosetting After spin coating, the acrylic plate is immediately placed in a thermostat controlled at 100 ° C. and heated for 10 minutes. Thereby, the silica sol is changed to SiO ₂ (inorganic oxide), and the thermosetting is completed. Thus, an acrylic plate having a hydrophilic film formed on the surface is completed.

(4) Evaluation experiment When the contact angle of the hydrophilic film with water was measured, it was 15 to 28 °. The pencil hardness of the hydrophilic film was 2H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 200 nm were confirmed. From the cross-sectional photograph, the void was 9 to 11% of the volume of the hydrophilic film.

  A hydrophilic film was formed on the acrylic plate in the same manner as in Example 1 except that methanol (15 parts by weight) was used instead of ethanol (15 parts by weight) when adjusting the hydrophilic film coating amount.

  When the contact angle of this membrane with water was measured, it was 15 to 28 °. The pencil hardness of the hydrophilic film was 3H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 200 nm were confirmed. The space | gap was 3 to 5% of the whole volume of the hydrophilic film | membrane from the cross-sectional photograph.

  A hydrophilic film was formed on the acrylic plate in the same manner as in Example 1 except that n-propanol (15 parts by weight) was used instead of ethanol (15 parts by weight) when preparing the hydrophilic paint.

  When the contact angle of this membrane with water was measured, it was 15 to 28 °. The pencil hardness of the hydrophilic film was 2H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 200 nm were confirmed. From the cross-sectional photograph, the gap was 12 to 14% of the entire volume of the hydrophilic film.

  A hydrophilic film was formed on the acrylic plate in the same manner as in Example 1 except that n-butanol (15 parts by weight) was used in place of ethanol (15 parts by weight) at the time of preparing the hydrophilic paint.

  When the contact angle of this membrane with water was measured, it was 15 to 28 °. The pencil hardness of the hydrophilic film was H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 200 nm were confirmed. From the cross-sectional photograph, the gap was 15 to 18% of the entire volume of the hydrophilic film.

  From Examples 1 to 4, it was shown that when the porosity is 14% or less, the hardness of the hydrophilic film is 2H or more.

  A hydrophilic film was formed in the same manner as in Example 1 except that a polycarbonate plate (manufactured by Kagaku Fujimoto) having the same size and thickness was used instead of the acrylic plate. The heat distortion temperature of the polycarbonate plate used was 110 ° C.

  When the contact angle of this membrane with water was measured, it was 15 to 28 °. The pencil hardness of the hydrophilic film was 2H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 200 nm were confirmed. From the cross-sectional photograph, the gap was 9 to 11% of the entire volume of the hydrophilic film. This indicates that a hydrophilic film having similar characteristics can be formed even when the resin is changed from acrylic to polycarbonate.

  A hydrophilic film was formed in the same manner as in Example 1 except that an operation of leaving on a hot plate at 80 ° C. for 5 minutes was added before thermosetting at 100 ° C.

  When the contact angle of this membrane with water was measured, it was 15 to 27 °. The pencil hardness of the hydrophilic film was 2H. When the cross section of the hydrophilic film was examined, voids having a size of 20 to 100 nm were confirmed. From the cross-sectional photograph, the gap was 2 to 3% of the entire volume of the hydrophilic film.

  When preparing the hydrophilic paint, methanol (15 parts by weight) is used instead of ethanol (15 parts by weight), and at the time of thermosetting, it is left on a hot plate at 80 ° C. for 5 minutes before being placed in a thermostat controlled at 100 ° C. A hydrophilic film was formed in the same manner as in Example 1 except for adding the operation.

  When the contact angle of this membrane with water was measured, it was 15 to 27 °. The pencil hardness of the hydrophilic film was H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 50 nm were confirmed. From the cross-sectional photograph, the voids were 0.6 to 0.8% of the entire volume of the hydrophilic film.

  From Examples 5 to 7, it was shown that when the porosity is 2% or more, the hardness of the hydrophilic film is 2H or more. Further, Examples 1 to 7 show that the hardness of the hydrophilic film is 2H or more when the porosity is 2% or more and 14% or less.

At the time of hydrophilic paint adjustment, silicone-based additive (BYK-Chemie BYK-370)
A hydrophilic film was formed in the same manner as in Example 1 except that (0.006 parts by weight) was added.

  When the contact angle of this membrane with water was measured, it was 20 to 26 °. The pencil hardness of the hydrophilic film was 3H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 200 nm were confirmed. From the cross-sectional photograph, the gap was 9 to 11% of the entire volume of the hydrophilic film.

At the time of hydrophilic paint adjustment, silicone-based additive (BYK-Chemie, BYK-310)
A hydrophilic film was formed in the same manner as in Example 1 except that (0.006 parts by weight) was added.

  When the contact angle of this membrane with water was measured, it was 20 to 27 °. The pencil hardness of the hydrophilic film was 3H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 200 nm were confirmed. From the cross-sectional photograph, the gap was 9 to 11% of the entire volume of the hydrophilic film.

  Next, a traverse test was performed in order to examine the abrasion resistance of the hydrophilic film. The test was performed under the condition of reciprocating up to 5000 times while visually checking the surface 1000 times (reciprocating) while applying a load of 100 g to a slider covered with a # 40 velvet cloth. The examined hydrophilic membranes are those produced in Examples 1, 8, and 9. As a result, the hydrophilic film produced in Example 1 was confirmed to be scratched due to film peeling on the surface after sliding 1000 times. However, the hydrophilic films prepared in Examples 8 and 9 had a contact angle with water of 25 to 29 ° after sliding 5000 times. Since the hydrophilic film produced in Example 1 was affected by scratches, a reproducible value of the contact angle was not obtained.

  From Examples 8 and 9, it was shown that the abrasion resistance of the hydrophilic coating film was greatly improved by adding a silicone additive.

  Except for using colloidal silica (Nissan Chemical IPA-ST) (2 parts by weight), hydrophilic alumina (Nissan Chemical No. 520) (2 parts by weight) instead of colloidal silica (2 parts by weight), the same procedure as in Example 1 was performed. A hydrophilic film was formed.

  When the contact angle of this membrane with water was measured, it was 18 to 26 °. The pencil hardness of the hydrophilic film was 2H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 200 nm were confirmed. From the cross-sectional photograph, the gap was 11 to 13% of the entire volume of the hydrophilic film.

However, the formed hydrophilic film was opaque. The light transmittances of 400 nm, 500 nm, 600 nm, and 700 nm of the hydrophilic films prepared in Examples 1 to 8 were all 90% or more (the wavelength in the visible region is 400 to 700 nm. The light transmittance is an index for examining the transparency of the film).

  However, the hydrophilic film produced in this example had a transmittance of 70% or less at any wavelength. The hydrophilic films prepared in Examples 1 to 8 were colloidal silica made of silicon oxide as a hydrophilic material, but hydrophilic alumina is used in this example. Therefore, from the above, it was shown that colloidal silica made of silicon oxide is preferable for producing a hydrophilic film in that it does not affect the light transmittance of the resin plate.

[Comparative Example 1]
A hydrophilic film was formed on the acrylic plate in the same manner as in Example 1 except that the hot plate on which the acrylic plate was placed was not heated during the pretreatment of the hydrophilic paint application. That is, only ultraviolet light irradiation was performed at the time of the pretreatment for applying the hydrophilic paint. When the contact angle of the hydrophilic film thus formed with water was measured, it was 15 to 28 °.

  However, the pencil hardness of the hydrophilic film was 2B. Moreover, the space | gap was 17 to 20% of the whole volume of the hydrophilic film from the cross-sectional photograph.

  According to Example 1 and this comparative example, it was shown that the hardness of the hydrophilic film is improved by using ultraviolet light irradiation and superheating treatment at the time of pretreatment of applying the hydrophilic paint.

  A method for producing a water-repellent film and evaluation results in this example will be described.

First, a hydrophilic film is formed on an acrylic plate in the same manner as in Example 1. The plate is immersed in a 0.1 wt% PF-5080 solution of Compound 1 for 1 hour. PF-5080 is a fluorine-based solvent manufactured by 3M. Moreover, since the specific gravity of this solution is as large as about 1.7, the acrylic plate (specific gravity 1) simply floats when it is dipped. When sinking, the corner of the acrylic plate is bonded to the bottom of the immersion bath in advance with a double-sided tape, and then a 0.1 wt% PF-5080 solution of Compound 1 is poured into the immersion bath to prevent the acrylic plate from being lifted. be able to.

  After immersion, the acrylic plate is left in a thermostatic bath at 95 ° C. for 1 hour. In this way, Compound 1 forms a chemical bond with the hydroxyl group on the hydrophilic film surface on the acrylic plate.

  The acrylic plate after heating for 1 hour is taken out of the thermostat and rinsed with PF-5080. Thereby, the compound 1 which is not chemically bonded to the hydrophilic film on the acrylic plate is removed. Thus, a water repellent film was formed on the acrylic plate.

  Next, the contact angle of the water repellent film with water was measured to be 113 °. The pencil hardness of the water repellent film was 3H.

  A water repellent film was formed on an acrylic plate in the same manner as in Example 11 except that a 0.1 wt% PF-5080 solution of compound 2 was used instead of a 0.1 wt% PF-5080 solution of compound 1. .

The contact angle of the water repellent film with water was measured to be 113 °. The pencil hardness of the water repellent film was 3H.

  A water repellent film was formed on an acrylic plate in the same manner as in Example 11 except that a 0.1 wt% PF-5080 solution of Compound 3 was used instead of the 0.1 wt% PF-5080 solution of Compound 1 .

The contact angle of the water repellent film with water was measured to be 113 °. The pencil hardness of the water repellent film was 3H.

  A water repellent film was formed on an acrylic plate in the same manner as in Example 11 except that a 0.1 wt% PF-5080 solution of Compound 1 was used instead of a 0.1 wt% PF-5080 solution of Compound 1 .

The contact angle of the water repellent film with water was measured to be 113 °. The pencil hardness of the water repellent film was 3H.

A water repellent film was formed on an acrylic plate in the same manner as in Example 11 except that a 0.05 wt% PF-5080 solution of compound 5 was used instead of a 0.1 wt% PF-5080 solution of compound 1. .

The contact angle of the water repellent film with water was measured to be 105 °. The pencil hardness of the water repellent film was 2H.

A water repellent film was formed on the acrylic plate in the same manner as in Example 11 except that a 0.05 wt% PF-5080 solution of compound 6 was used instead of a 0.1 wt% PF-5080 solution of compound 1. .

The contact angle of the water repellent film with water was measured to be 105 °. The pencil hardness of the water repellent film was 2H.

A water repellent film was formed on an acrylic plate in the same manner as in Example 11 except that a 0.05 wt% PF-5080 solution of compound 7 was used instead of a 0.1 wt% PF-5080 solution of compound 1. .

The contact angle of the water repellent film with water was measured and found to be 107 °. The pencil hardness of the water repellent film was 2H.

A water repellent film was formed on an acrylic plate in the same manner as in Example 11 except that a 0.05 wt% PF-5080 solution of compound 8 was used instead of a 0.1 wt% PF-5080 solution of compound 1. .

The contact angle of the water repellent film with water was measured and found to be 107 °. The pencil hardness of the water repellent film was 2H.

A water repellent film was formed on an acrylic plate in the same manner as in Example 11 except that a 0.05 wt% PF-5080 solution of compound 9 was used instead of a 0.1 wt% PF-5080 solution of compound 1. .

The contact angle of the water repellent film with water was measured to be 111 °. The pencil hardness of the water repellent film was 3H.

  A water repellent film was formed on an acrylic plate in the same manner as in Example 11 except that a 0.05 wt% PF-5080 solution of compound 10 was used instead of a 0.1 wt% PF-5080 solution of compound 1. .

The contact angle of the water repellent film with water was measured to be 112 °. The pencil hardness of the water repellent film was 3H.

  A water repellent film was formed on an acrylic plate in the same manner as in Example 11 except that a 0.05 wt% PF-5080 solution of Compound 11 was used instead of a 0.1 wt% PF-5080 solution of Compound 1. .

The contact angle of the water repellent film with water was measured to be 111 °. The pencil hardness of the water repellent film was 3H.

  A water repellent film was formed on an acrylic plate in the same manner as in Example 11 except that a 0.05 wt% PF-5080 solution of Compound 12 was used instead of a 0.1 wt% PF-5080 solution of Compound 1. .

The contact angle of the water repellent film with water was measured to be 112 °. The pencil hardness of the water repellent film was 3H.

  A water repellent film was formed on the hydrophilic film prepared in Example 10 instead of the hydrophilic film prepared in Example 1. That is, the same as Example 1 except that hydrophilic alumina (Nissan Chemical No. 520) (2 parts by weight) is used instead of colloidal silica (IPA-ST, Nissan Chemical Co., Ltd.) (2 parts by weight) at the time of preparing the hydrophilic paint. The hydrophilic film formed as described above was used. The water-repellent film was prepared in the same manner as in Example 11 using a 0.1 wt% PF-5080 solution of Compound 1 as in Example 11.

  The contact angle of the produced water repellent film with water was measured to be 113 °. The pencil hardness of the water repellent film was 3H.

  The formed water repellent film was opaque. This is because the underlying hydrophilic film is opaque.

  The 400 nm, 500 nm, 600 nm, and 700 nm light transmittances of the water repellent film produced in Example 11 were all 90% or more, but the water repellent film produced in this example was transmissive at any wavelength. The rate was 70% or less. This is because the hydrophilic film produced in Example 11 uses colloidal silica made of silicon oxide as a hydrophilic material, whereas this example uses hydrophilicity. Therefore, from the above, it was shown that colloidal silica made of silicon oxide is preferable for producing a water-repellent film in that it does not affect the light transmittance of the resin plate.

  When the acrylic plate formed with the water repellent film produced in Examples 11 to 22 was pulled up after being immersed in gasoline having an octane number of 95 for 100 hours, the water repellent film produced in Examples 11 to 14 repelled ethanol. The water-repellent films produced in Examples 15 to 22 were wet without repelling ethanol.

  The fluorine-containing compounds (Compounds 1 to 4) used in Examples 11 to 14 have perfluoropolyether chains, but the cancer fluorine compounds (Compounds 5 to 12) used in Examples 15 to 22 are perfluoro. Does not have a polyether chain.

  From the above, it was shown that a water-repellent film using a compound having a perfluoropolyether chain as a fluorine-containing compound can form a film that can be easily repelled against an organic solvent.

When the acrylic plate formed with the water repellent film produced in Example 23 was immersed in gasoline having an octane number of 95 for 100 hours and then pulled up, the water repellent film repelled gasoline. I dipped it in ethanol for 100 hours instead of gasoline and pulled it up. Therefore, a water-repellent film using a compound having a perfluoropolyether chain as a fluorine-containing compound can play against organic solvents even if the underlying hydrophilic film contains an inorganic oxide other than silicon oxide. It was shown that an easy film can be formed.

  In the pretreatment for applying the hydrophilic paint, a hydrophilic film was formed on the acrylic plate in the same manner as in Example 1 except that the irradiation light amount was 55 mW, the irradiation time was 1 minute, and the temperature of the hot plate was 120 ° C. .

  When the contact angle of this membrane with water was measured, it was 15 to 28 °. The pencil hardness of the hydrophilic film was 2H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 200 nm were confirmed. The space | gap was 3 to 5% of the whole volume of the hydrophilic film | membrane from the cross-sectional photograph.

  Further, a hydrophilic film was formed on the acrylic plate in the same manner as in Example 1 except that the temperature of the hot plate was set to 80 ° C. in the pretreatment of the hydrophilic paint.

  When the contact angle of this membrane with water was measured, it was 15 to 28 °. The pencil hardness of the hydrophilic film was 2H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 200 nm were confirmed. The space | gap was 3 to 5% of the whole volume of the hydrophilic film | membrane from the cross-sectional photograph.

[Comparative Example 2]
In the pretreatment for applying the hydrophilic paint, a hydrophilic film was formed on the acrylic plate in the same manner as in Example 1 except that the irradiation light amount was 55 mW, the irradiation time was 1 minute, and the temperature of the hot plate was 125 ° C. .

  When the contact angle of this membrane with water was measured, it was 15 to 28 °. The pencil hardness of the hydrophilic film was 2H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 200 nm were confirmed. The space | gap was 3 to 5% of the whole volume of the hydrophilic film | membrane from the cross-sectional photograph.

However, the acrylic plate was thermally deformed during the pretreatment of applying the hydrophilic paint. Therefore, when the same treatment was performed with the light irradiation time being 45 seconds, the surface of the acrylic plate repels the hydrophilic paint, and uniform paint application could not be performed. Therefore, the formed hydrophilic film was visually confirmed to be smeared.

  Further, a hydrophilic film was formed on the acrylic plate in the same manner as in Example 1 except that the temperature of the hot plate was 75 ° C. in the pretreatment of the hydrophilic paint.

  When the contact angle of this membrane with water was measured, it was 15 to 28 °. The pencil hardness of the hydrophilic film was HB. The heat distortion temperature of the used acrylic board is 100 degreeC.

  From this comparative example and Example 26, it is shown that when the resin is an acrylic plate in the pretreatment of applying the hydrophilic paint, it is preferable that the heating temperature at the time of ultraviolet light irradiation is the heat distortion temperature ± 20 ° C. It was.

  In the pretreatment for applying the hydrophilic paint, a hydrophilic film was formed on the polycarbonate plate in the same manner as in Example 5 except that the irradiation light amount was 55 mW, the irradiation time was 1 minute, and the temperature of the hot plate was 130 ° C. .

  When the contact angle of this membrane with water was measured, it was 15 to 28 °. The pencil hardness of the hydrophilic film was 2H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 200 nm were confirmed. From the cross-sectional photograph, the gap was 9 to 11% of the entire volume of the hydrophilic film.

[Comparative Example 3]
In the pretreatment for applying the hydrophilic paint, a hydrophilic film was formed on the polycarbonate plate in the same manner as in Example 5 except that the irradiation light amount was 55 mW, the irradiation time was 1 minute, and the temperature of the hot plate was 135 ° C. .

  When the contact angle of this membrane with water was measured, it was 15 to 28 °. The pencil hardness of the hydrophilic film was 2H.

  However, the polycarbonate plate was thermally deformed in the pretreatment for applying the hydrophilic paint. Then, when the same treatment was carried out with the light irradiation time being 45 seconds, the surface of the polycarbonate plate repels the hydrophilic paint and the uniform paint could not be applied. Therefore, the formed hydrophilic film was visually confirmed to be smeared.

  Further, a hydrophilic film was formed on the polycarbonate plate in the same manner as in Example 5 except that the temperature of the hot plate was 85 ° C. in the pretreatment of the hydrophilic paint.

  When the contact angle of this membrane with water was measured, it was 15 to 28 °. However, the pencil hardness of the hydrophilic film was HB. The heat distortion temperature of the used polycarbonate plate is 110 ° C.

  From this comparative example and Example 27, it was shown that in the pretreatment for applying the hydrophilic paint, it is preferable that the heating temperature at the time of ultraviolet light irradiation is the heat distortion temperature ± 20 ° C.

  Acrylic board in the same manner as in Example 1 except that, when preparing the hydrophilic film paint, Silaace S310 (0.1 part by weight) manufactured by Chisso Corporation, which is a kind of alkoxysilane having an amino group, is used instead of silica sol (1 part by weight). A hydrophilic film was formed on the substrate. In addition, Silaace S310 is polymerized by heating during film formation, and becomes a polymer of alkoxysilane having an amino group.

  When the contact angle of this membrane with water was examined, it was 15 to 28 °. The pencil hardness of the hydrophilic film was 2H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 200 nm were confirmed. The space | gap was 3 to 5% of the whole volume of the hydrophilic film | membrane from the cross-sectional photograph.

  This acrylic plate was left in a glass desiccator having a capacity of 10 liters with 100 ml of 10% by weight hydrochloric acid at the bottom for one day. The purpose of this is to leave the acrylic plate in an acidic atmosphere. The acrylic plate taken out from the desiccator was washed with water, dried, and the contact angle of the hydrophilic film with water was measured. That is, the hydrophilicity of the hydrophilic film was improved.

  Acrylic plate in the same manner as in Example 1 except that when preparing the hydrophilic film paint, Silaace S320 (0.1 part by weight) manufactured by Chisso Corporation, which is a kind of alkoxysilane having an amino group, is used instead of silica sol (1 part by weight). A hydrophilic film was formed on the substrate. In addition, Silaace S320 is polymerized by heating during film formation, and becomes an alkoxysilane polymer having an amino group.

  When the contact angle of this membrane with water was examined, it was 14 to 26 °. The pencil hardness of the hydrophilic film was 2H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 200 nm were confirmed. The space | gap was 3 to 5% of the whole volume of the hydrophilic film | membrane from the cross-sectional photograph.

  This acrylic plate was left in a glass desiccator having a capacity of 10 liters with 100 ml of 10% by weight hydrochloric acid at the bottom for one day. The purpose of this is to leave the acrylic plate in an acidic atmosphere. The acrylic plate taken out from the desiccator was washed with water, dried, and the contact angle of the hydrophilic film with water was measured. That is, the hydrophilicity of the hydrophilic film was improved.

  Acrylic board in the same manner as in Example 1 except that when preparing the hydrophilic film paint, Silaace S330 (0.1 part by weight) manufactured by Chisso Corporation, which is a kind of alkoxysilane having an amino group, is used instead of silica sol (1 part by weight). A hydrophilic film was formed on the substrate. Note that Silaace S330 is polymerized by heating during film formation, and becomes an alkoxysilane polymer having an amino group.

  When the contact angle of this membrane with water was examined, it was 15 to 26 °. The pencil hardness of the hydrophilic film was 2H.

  When the cross section of the hydrophilic film was examined, voids having a size of 20 to 200 nm were confirmed. The space | gap was 3 to 5% of the whole volume of the hydrophilic film | membrane from the cross-sectional photograph.

  This acrylic plate was left in a glass desiccator having a capacity of 10 liters with 100 ml of 10% by weight hydrochloric acid at the bottom for one day. The purpose of this is to leave the acrylic plate in an acidic atmosphere. The acrylic plate taken out from the desiccator was washed with water and dried, and when the contact angle of the hydrophilic film with water was measured, it decreased to 10 to 15 °. That is, the hydrophilicity of the hydrophilic film was improved.

  Examples 28-30 showed that when the film has an alkoxysilane polymer having an amino group, the hydrophilicity can be improved by leaving it in an acidic atmosphere.

A cross-sectional photograph of a hydrophilic film formed on a resin. (A) Intensity of elements in the island-shaped region of the hydrophilic film, (B) Intensity of elements in other than the island-shaped region of the hydrophilic film.

Claims (5)

A resin plate having a hydrophilic film,
The hydrophilic film is formed on the resin plate,
A water repellent film is formed on the hydrophilic film,
The hydrophilic film has a void having a size of 20 nm to 200 nm,
The water repellent film is formed by including a material having the following structure.

A resin plate having a hydrophilic film,
The hydrophilic film is formed on the resin plate,
A water repellent film is formed on the hydrophilic film,
The hydrophilic film has a void having a size of 20 nm to 200 nm,
The water repellent film is formed by including a material having the following structure.

  The resin plate according to claim 1, wherein the hydrophilic film is formed of silicon oxide.   The resin plate according to any one of claims 1 to 3, wherein the volume ratio of the voids is 2% or more and 14% or less of the entire volume of the hydrophilic film. 5. The resin plate according to claim 1, wherein the hydrophilic film is formed on the resin plate by applying a liquid in which at least silica sol and colloidal silica are mixed.

Images