JP7087461B2 - Mold release treatment solution and film manufacturing method - Google Patents

Description

The present invention relates to a mold release treatment solution and a method for producing a film.

An article having a fine concavo-convex structure with a pitch equal to or lower than the wavelength of visible light on its surface exhibits an antireflection function and the like, and therefore its usefulness is attracting attention. In particular, it is known that a fine concavo-convex structure called a moth-eye structure exhibits an effective antireflection function by continuously increasing from the refractive index of air to the refractive index of the material. ..

As a method for manufacturing an article having a fine uneven structure on the surface, for example, a method for directly processing the surface of a transparent base material or the like to manufacture an article having a fine uneven structure on the surface, and an inverted structure corresponding to the fine uneven structure are provided. A method of transferring the inverted structure to the surface of a transparent substrate or the like using a mold can be mentioned, but from the viewpoint of productivity and economy, a transparent group is used by using a mold having an inverted structure corresponding to a fine uneven structure. A method of transferring the inverted structure to the surface of a material or the like is often used.

Examples of the method for forming the inverted structure by the mold include an electron beam drawing method and a laser light interferometry. In recent years, as a method for forming the inverted structure more easily, the surface of the aluminum base material is anodized. Attention is being paid to how to do this. The anodized alumina formed by anodizing the surface of the aluminum base material is an aluminum oxide film (anodized) and has a plurality of pores (fine concavo-convex structure) having a pitch equal to or lower than the wavelength of visible light.

By the way, when an article having a fine concavo-convex structure on the surface is manufactured by a method of transferring the inverted structure to the surface of a transparent base material or the like using a mold having an inverted structure corresponding to the fine concavo-convex structure, the mold and the article are used. Since the contact interface is greatly increased, there is a problem that it is difficult to release the mold.

As a method for solving the above-mentioned problems, for example, in Patent Document 1, a mold release treatment solution in which a phosphorus compound is dissolved in water or a mold release treatment solution in which a phosphorus compound is dissolved in an organic solvent is applied to the mold surface. A method of applying and producing an article having a fine uneven structure on the surface has been proposed.

International Publication 2012/161315 Pamphlet

However, in the production method disclosed in Patent Document 1, when a mold release treatment solution in which a phosphorus compound is dissolved in water is used, when the mold release treatment solution is applied to the mold surface, the mold is molded. Since most of the dirt adhering to the surface does not come off and remains as it is, there is a problem that defects occur in the article having the obtained fine uneven structure on the surface. In addition, the wettability to the mold is poor, it is difficult to release the fine uneven structure evenly, causing local mold release defects, and the optical strain of the article having the obtained fine uneven structure on the surface. Has the problem of occurring. In addition, if the mold release treatment solution in which the phosphorus compound is dissolved in water is stored, mold may be generated in the solution and in the container, piping, filter, etc. where the solution remains. When the mold is demolded with a solution in which mold is generated, the mold may adhere to the mold and spore-like fine uneven structure may be lost, resulting in defects. Further, there is a problem that the number of types of phosphorus compounds that can be dissolved in water is small, and the mold release treatment solution that can be prepared is limited.
In addition, when a mold release treatment solution in which a phosphorus compound is dissolved in an organic solvent is used, the mold release treatment solution volatilizes during the mold release treatment, and the concentration of the mold release treatment solution increases due to the volatilization. It changes over time and causes uneven application of the mold release treatment solution to the mold surface. If the volatility is higher, moisture in the air will condense and fine water droplets will adhere to the surface of the mold, causing uneven application of the mold release treatment solution to the surface of the mold. Such coating unevenness has a problem that local mold release defects occur during the production of an article having a fine uneven structure on the surface, and optical distortion of the article having the obtained fine uneven structure on the surface occurs. Further, the mold release treatment solution using a highly volatile organic solvent has a problem that the concentration tends to change with time and it is difficult to control the concentration of the mold release treatment solution. Furthermore, many organic solvents fall under the category of dangerous goods, and when organic solvents that fall under the category of dangerous goods are used, there is a risk of handling dangerous goods, and a heavy manufacturing facility that handles the dangerous goods must be designed. It has the problem of not becoming.

Therefore, the present invention solves these problems, can remove stains adhering to the surface of the mold, can suppress uneven coating on the surface of the mold, and can release the mold with excellent mold releasability. The purpose is to provide a treatment solution.
Further, the present invention is to provide a method for producing a film having excellent releasability, which can obtain a film having excellent quality stability.

The present invention has the following aspects.
[1] A mold release treatment solution containing a poly) oxyalkylene alkyl phosphoric acid compound (A) and a solvent (B), wherein the solvent (B) contains an organic solvent and water. Treatment solution.
[2] The mold release treatment solution according to [1], wherein the content of water in the solvent (B) is 5% by mass to 95% by mass.
[3] The mold release treatment solution according to [1] or [2], wherein the organic solvent is a water-soluble solvent.
[4] The organic solvent is at least one selected from the group consisting of ethanol, 1-propanol, isopropanol, ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether and N-methyl-2-pyrrolidone. The mold release treatment solution according to [3].
[5] The mold release treatment solution according to any one of [1] to [4], wherein the (poly) oxyalkylene alkyl phosphoric acid compound (A) is a compound represented by the following formula (1).
(HO) _3-n (O =) P [-O- (R ² O) _m -R ¹ ] _n ... (1)
(In the formula, R ¹ is an alkyl group, R ² is an alkylene group, m is an integer of 1 to 20, and n is an integer of 1 to 3.)
[6] The mold release treatment solution according to [5], wherein the (poly) oxyalkylene alkyl phosphoric acid compound (A) is (poly) oxyethylene alkyl ether phosphoric acid.
[7] The mold release treatment solution according to any one of [1] to [6], wherein the mold is a mold for forming an uneven structure by transfer.
[8] The mold release treatment solution according to [7], wherein the uneven structure is a moth-eye structure.
[9] A method for producing a film, which comprises the following steps (1) to (3) in sequence.
Step (1): A step of applying the mold release treatment solution according to any one of [1] to [8] to the mold surface.
Step (2): A step of supplying the curable composition to the surface of the mold and curing the curable composition.
Step (3): A step of peeling the cured product from the mold.
[10] The method for producing a film according to [9], wherein the mold is a mold for forming an uneven structure by transfer.
[11] The method for producing a film according to [10], wherein the uneven structure is a moth-eye structure.

The mold release treatment solution of the present invention can remove stains adhering to the mold surface, suppress uneven coating on the mold surface, and have excellent mold release properties.
Further, the film manufacturing method of the present invention can obtain a film having excellent quality stability and is excellent in releasability.

It is a schematic cross-sectional view which shows the manufacturing process which forms the anodized porous alumina which has a plurality of pores on the surface. It is a schematic cross-sectional view which shows the manufacturing apparatus of the film which has the concavo-convex structure on the surface. It is a schematic cross-sectional view which shows an example of the film which has the concavo-convex structure on the surface.

(Mold processing solution)
The mold treatment solution of the present invention contains a (poly) oxyalkylene alkyl phosphate compound (A) and a solvent (B).
The mold treatment solution of the present invention is preferably a uniform solution, preferably free of suspended matter and turbidity, because it can suppress defects in the film having a concavo-convex structure on its surface.
The mold treatment solution of the present invention may contain an antifoaming agent or the like for the purpose of improving handleability.

((Poly) Oxyalkylene alkyl phosphate compound (A))
The (poly) oxyalkylene alkyl phosphoric acid compound means an oxyalkylene alkyl phosphoric acid compound having one oxyalkylene group or a polyoxyalkylene alkyl phosphoric acid compound having two or more oxyalkylene groups.
Since the (poly) oxyalkylene alkyl phosphoric acid compound (A) is excellent in releasability, the compound represented by the following formula (1) is preferable, and (poly) oxyethylene alkyl ether phosphoric acid is more preferable.
(HO) _3-n (O =) P [-O- (R ² O) _m -R ¹ ] _n ... (1)
(In the formula, R ¹ is an alkyl group, R ² is an alkylene group, m is an integer of 1 to 20, and n is an integer of 1 to 3.)

Although R ¹ is an alkyl group, it is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 3 to 18 carbon atoms, and 4 to 4 carbon atoms because it is excellent in solubility in the solvent (B). 16 is more preferable, and 6 to 15 carbon atoms are particularly preferable.

Although R ² is an alkylene group, it is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 2 to 3 carbon atoms, and an ethylene group or propylene because it is excellent in solubility in the solvent (B). Groups are more preferred, and ethylene groups are particularly preferred.

Although m is an integer of 1 to 20, an integer of 1 to 10 is preferable because it is excellent in solubility in the solvent (B).

n is an integer of 1 to 3.
The (poly) oxyalkylene alkyl phosphoric acid compound (A) may be any of a monoester body (n = 1), a diester body (n = 2), and a triester body (n = 3). Further, in the case of an ester form or a triester form, a plurality of (poly) oxyalkylene alkyl groups in one molecule may be the same or different.

As the (poly) oxyalkylene alkyl phosphoric acid compound (A), a commercially available product may be used. As a commercially available product of the (poly) oxyalkylene alkyl phosphate compound (A), for example, JP-506H (trade name, manufactured by Johoku Chemical Industry Co., Ltd., R ¹ : butyl group, R ² : ethylene group, m≈1 , N≈1-2), Moldwith INT-1856 (trade name, manufactured by Axel), TDP-10 (trade name, manufactured by Nikko Chemicals Co., Ltd., R ¹ : Alkyl group having 12 to 15 carbon atoms, R ² : Ethylene group, m≈10, n≈3), TDP-8 (trade name, manufactured by Nikko Chemicals Co., Ltd., ^R1 : alkyl group with 12 to 15 carbon atoms, ^R2 : ethylene group, m≈8, n ≈3), TDP-6 (trade name, manufactured by Nikko Chemicals Co., Ltd., ^R1 : alkyl group with 12 to 15 carbon atoms, ^R2 : ethylene group, m≈6, n≈3), TDP-2 (commodity) Name, manufactured by Nikko Chemicals Co., Ltd., R ¹ : alkyl group having 12 to 15 carbon atoms, R ² : ethylene group, m≈2, n≈3), DDP-10 (trade name, manufactured by Nikko Chemicals Co., Ltd., R ¹ : Alkyl group having 12 to 15 carbon atoms, R ² : Ethylene group, m≈10, n≈2), DDP-8 (trade name, manufactured by Nikko Chemicals Co., Ltd., ^R1 : 12 to 15 carbon atoms Alkyl group, R ² : Ethylene group, m≈8, n≈2), DDP-6 (trade name, manufactured by Nikko Chemicals Co., Ltd., ^R1 : alkyl group having 12 to 15 carbon atoms, ^R2 : ethylene group, m≈6, n≈2), DDP-4 (trade name, manufactured by Nikko Chemicals Co., Ltd., ^R1 : alkyl group having 12 to 15 carbon atoms, ^R2 : ethylene group, m≈4, n≈2), DDP-2 (trade name, manufactured by Nikko Chemicals Co., Ltd., R ¹ : alkyl group having 12 to 15 carbon atoms, R ² : ethylene group, m≈2, n≈2), TLP-4 (trade name, Nikko Chemicals) Made by R ¹ : Lauryl group, R ² : Ethylene group, m ≈ 4, n ≈ 3), TCP-5 (trade name, manufactured by Nikko Chemicals Co., Ltd., R ¹ : Ethylene group, R ² : Ethylene Group, m≈5, n≈3), DLP-10 (trade name, manufactured by Nikko Chemicals Co., Ltd., ^R1 : lauryl group, ^R2 : ethylene group, m≈10, n≈3) and the like. Among the commercially available products of these (poly) oxyalkylene alkyl phosphoric acid compounds (A), TDP-10, TDP-8, and TDP-6 are excellent in releasability and solubility in the solvent (B). , TDP-2 is preferable, and TDP-8 and TDP-2 are more preferable.

As the (poly) oxyalkylene alkyl phosphoric acid compound (A), one type may be used alone, or two or more types may be used in combination.

(Solvent (B))
The solvent (B) includes an organic solvent and water.

Examples of the organic solvent include alcohols such as methanol, ethanol, 1-propanol, isopropanol, t-butanol, 1,4-butanediol, 1,3-butanediol, ethylene glycol, propylene glycol and glycerin; acetone and methyl ethyl ketone. Etc .; ethers such as 1,4-dioxane, tetrahydrofuran, 1,3-dioxolane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; esters such as ethyl acetate, butyl acetate, γ-butyrolactone; methyl lactate, ethyl lactate, etc. Lactates; Glycol ethers such as diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and triethylene glycol monomethyl ether. Glycol esters such as diethylene glycol monoethyl ether acetate; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, acetonitrile; sulfur-containing solvents such as dimethylsulfoxide; aliphatic hydrocarbons such as hexane and heptane Kind; Examples include aromatic hydrocarbons such as benzene and toluene. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, water-soluble solvents are preferable because they have excellent compatibility with water, and ethanol, 1-propanol, isopropanol, ethylene glycol, acetone, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and triethylene glycol monomethyl ether are preferable. , N-Methyl-2-pyrrolidone is more preferred, and 1-propanol, isopropanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, and N-methyl-2-pyrrolidone are even more preferred.
In the present specification, the water-soluble solvent refers to a solvent that can maintain a uniform appearance without separation when mixed with the same volume of water under the conditions of 1 atm and 20 ° C. Further, in the present specification, the water-insoluble solvent means a solvent other than the water-soluble solvent.

The content of water in the solvent (B) is preferably 5% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and 40% by mass to 85% by mass in 100% by mass of the solvent (B). More preferred. When the content of water in the solvent (B) is 5% by mass or more, the change in the concentration of the mold release treatment solution with time can be suppressed, and the mold release treatment solution can be applied to the mold surface. It is possible to suppress coating unevenness of the film, and the quality stability of the film having the obtained uneven structure on the surface is excellent. Further, when the content of water in the solvent (B) is 95% by mass or less, dirt adhering to the mold surface can be removed, and defects of the film having the obtained uneven structure on the surface can be suppressed. can.

The content of the organic solvent in the solvent (B) is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 80% by mass, and 15% by mass to 60% by mass in 100% by mass of the solvent (B). Is more preferable. When the content of the organic solvent in the solvent (B) is 5% by mass or more, stains adhering to the mold surface can be removed, and defects of the film having the obtained uneven structure on the surface can be suppressed. .. Further, when the content of the organic solvent in the solvent (B) is 5% by mass or more, the generation of mold can be suppressed, so that defects due to mold adhesion can be prevented. Regarding the suppression of mold growth, the higher the content of the organic solvent, the higher the effect, and the lower the content, the lower the effect. Further, when the content of the organic solvent in the solvent (B) is 95% by mass or less, the change in the concentration of the mold release treatment solution with time can be suppressed, and the mold of the mold release treatment solution can be suppressed. It is possible to suppress uneven coating on the mold surface, and the quality stability of the film having the obtained uneven structure on the surface is excellent.

The content of the water-soluble solvent in the organic solvent is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 95% by mass in 100% by mass of the organic solvent. When the content of the water-soluble solvent in the organic solvent is 50% by mass or more, the compatibility between the organic solvent and water is excellent. Further, when the content of the water-soluble solvent in the organic solvent is 95% by mass or less, the types of the (poly) oxyalkylene alkyl phosphoric acid compound (A) that can be selected increase.

The content of the water-insoluble solvent in the organic solvent is preferably 0% by mass to 50% by mass, more preferably 5% by mass to 40% by mass in 100% by mass of the organic solvent. When the content of the water-insoluble solvent in the organic solvent is 5% by mass or more, the types of the (poly) oxyalkylene alkyl phosphoric acid compound (A) that can be selected increase. Further, when the content of the water-insoluble solvent in the organic solvent is 50% by mass or less, the compatibility between the organic solvent and water is excellent.

(Mold)
Since the mold needs the effect of the present invention more, a mold for forming an uneven structure by transfer is preferable.

Examples of the uneven structure include a prism structure, a microlens structure, a moth-eye structure, and the like. Among these uneven structures, the moth-eye structure is preferable because the effect of the present invention is more required.

As a method for manufacturing a mold, for example, a method of providing an inverted structure of an uneven structure on the surface by a lithography method, a method of providing an inverted structure of an uneven structure on the surface by laser processing, and a method of providing anodized porous alumina having a plurality of pores on the surface. Examples thereof include a method of forming the surface and a method of replicating from a mother die having an uneven structure by an electroplating method or the like. Among these mold manufacturing methods, the effect of the present invention is more required, and the (poly) oxyalkylene alkyl phosphate compound (A) interacts with alumina to exhibit more mold releasability. A method of forming anodized porous alumina having pores on the surface is more preferable.

The method of forming anodized porous alumina having a plurality of pores on the surface easily includes the following steps (a) to (f) because the uneven structure is easy to control and the mold productivity is excellent. Is preferable.
Step (a): A step of anodizing an aluminum base material in an electrolytic solution under a constant voltage to form an oxide film on the surface of the aluminum base material.
Step (b): A step of removing a part or all of the oxide film to form an anodizing pore generation point on the surface of the aluminum substrate.
Step (c): A step of anodizing the aluminum base material again in the electrolytic solution to form an oxide film having pores at the pore generation points.
Step (d): A step of expanding the diameter of the pores.
Step (e): A step of anodizing again in the electrolytic solution.
Step (f): A step of repeating step (d) and step (e) to obtain a mold having anodized porous alumina having a plurality of pores on the surface.

FIG. 1 is a schematic cross-sectional view showing a manufacturing process for forming anodized porous alumina having a plurality of pores on the surface. Hereinafter, steps (a) to (f) will be described with reference to FIG. 1, but the method for forming anodized porous alumina having a plurality of pores on the surface is not limited to FIG.

(Step (a))
The step (a) is a step of anodizing the aluminum base material in an electrolytic solution under a constant voltage to form an oxide film on the surface of the aluminum base material. As shown in FIG. 1, when the aluminum base material 10 is anodized, an oxide film 14 having pores 12 is formed.

Examples of the shape of the aluminum base material include a roll shape, a circular tubular shape, a flat plate shape, and a sheet shape. Among these shapes of the aluminum base material, a roll shape and a circular tubular shape are preferable, and a roll shape is more preferable, because the film having an uneven structure on the surface is excellent in productivity.

The aluminum substrate is preferably polished to smooth the surface.
Examples of the polishing method include mechanical polishing, chemical polishing, chemical mechanical polishing, feather cloth polishing, electrolytic polishing and the like. As these polishing methods, one kind may be used alone, or two or more kinds may be used in combination. Among these polishing methods, mechanical polishing, chemical polishing, chemical mechanical polishing, and electrolytic polishing are preferable, and chemical mechanical polishing is more preferable, because the surface smoothness of the aluminum base material is excellent.

In chemical mechanical polishing (CMP polishing), a mixed solution of acid or alkali and water, and a polishing solution containing a polishing agent are embedded in a polishing body such as cloth, paper, or metal, and / or subject to polishing. By supplying a polishing liquid between the polishing bodies and rubbing the aluminum base material with the polishing body, the base material is scraped by the sharp part of the polishing agent contained in the polishing liquid, and aluminum is used with an acid or an alkali. This is a polishing method for smoothing the surface of a base material.

Since the aluminum base material may have oil attached to it when it is processed into a predetermined shape, it is preferable to perform degreasing treatment in advance before anodizing.

The purity of aluminum in the aluminum base material suppresses the formation of uneven structures of a size that scatters visible light due to segregation of impurities during anodizing, and the regularity of pores obtained by anodizing is reduced. This can be suppressed, so 99% or more is preferable, 99.5% or more is more preferable, and 99.8% or more is particularly preferable.

Examples of the electrolytic solution include sulfuric acid, oxalic acid, phosphoric acid and the like. These electrolytic solutions may be used alone or in combination of two or more. Among these electrolytic solutions, oxalic acid is preferable because it can form pores having a size equal to or smaller than the wavelength of visible light with high regularity.

When sulfuric acid is used as the electrolytic solution, the concentration of sulfuric acid is preferably 0.7 M or less because the current value does not become too high and a constant voltage can be maintained.
When sulfuric acid is used as the electrolytic solution, when the chemical conversion voltage is 25 V to 30 V, anodized alumina having highly regular pores having a period of 63 nm can be obtained. When the chemical conversion voltage is in this range, the regularity of the pores is excellent.
When sulfuric acid is used as the electrolytic solution, the temperature of the electrolytic solution is preferably 30 ° C. or lower, preferably 20 ° C., because it can prevent the pores from being broken or the surface from melting and the regularity of the pores being disturbed. The following is more preferable.

When oxalic acid is used as the electrolytic solution, the concentration of oxalic acid is preferably 0.7 M or less because the current value does not become too high and the surface of the oxide film can be suppressed from becoming rough.
When oxalic acid is used as the electrolytic solution, when the chemical conversion voltage is 30 V to 60 V, anodized alumina having highly regular pores having a period of 100 nm can be obtained. When the chemical conversion voltage is in this range, the regularity of the pores is excellent.
When oxalic acid is used as the electrolytic solution, the temperature of the electrolytic solution is preferably 60 ° C. or lower because it can prevent the pores from being broken or the surface from melting and the regularity of the pores being disturbed. ℃ or less is more preferable.

When phosphoric acid is used as the electrolytic solution, the concentration of phosphoric acid is preferably 0.5 M or less because the current value does not become too high and the surface of the oxide film can be suppressed from becoming rough.
When phosphoric acid is used as the electrolytic solution, when the chemical conversion voltage is 180 V to 220 V, anodized alumina having highly regular pores having a period of 500 nm can be obtained. When the chemical conversion voltage is in this range, the regularity of the pores is excellent.
When phosphoric acid is used as the electrolytic solution, the temperature of the electrolytic solution is preferably 30 ° C. or lower because it can prevent the pores from being broken or the surface from melting and the regularity of the pores being disturbed. ℃ or less is more preferable.

The step (b) is a step of removing a part or all of the oxide film and forming a pore generation point of anodization on the surface of the aluminum base material. As shown in FIG. 1, by temporarily removing a part or all of the oxide film 14 and setting it as the anodizing pore generation point 16, the regularity of the pores can be enhanced. The oxide film 14 fulfills the purpose of removing the oxide film even if a part of the oxide film 14 is not completely removed and a part of the oxide film 14 already has a sufficiently enhanced regularity. be able to.

Since the method for removing the oxide film can maintain the shape of the pore generation point formed in the step (a), the aluminum is not dissolved but is dissolved in a solution that selectively dissolves the oxide film to remove the oxide film. The method of doing is preferable. A solution that does not dissolve aluminum and selectively dissolves the oxide film is preferably a mixed solution of chromic acid and phosphoric acid because it has excellent dissolution selectivity.

(Step (c))
The step (c) is a step of anodizing the aluminum base material again in the electrolytic solution to form an oxide film having pores at the pore generation points. As shown in FIG. 1, when the aluminum base material 10 from which the oxide film 14 has been removed is anodized again, an oxide film 14 having columnar pores 12 is formed.

The anodization in the step (c) may be performed under the same conditions as in the step (a). The longer the anodizing time, the deeper the pores can be obtained. As long as the effect of the step (b) is not lost, the voltage of anodizing in the step (c), the type of the electrolytic solution, the temperature and the like can be appropriately set.

(Step (d))
The step (d) is a step of expanding the diameter of the pores. As shown in FIG. 1, a process of enlarging the diameter of the pore 12 (hereinafter, may be referred to as a “pore diameter enlargement process”) is performed.

The pore diameter enlargement treatment is a treatment for enlarging the diameter of the pores obtained by anodizing by immersing in a solution that dissolves the oxide film. The solution for dissolving the oxide film is preferably an aqueous solution of phosphoric acid because it has excellent solubility of aluminum oxide. The concentration of the aqueous phosphoric acid solution is preferably 1% by mass to 10% by mass because the dissolution rate can be easily controlled. The longer the pore diameter enlargement treatment time, the larger the pore diameter.

(Step (e))
The step (e) is a step of anodizing again in the electrolytic solution. As shown in FIG. 1, when anodized again, columnar pores 12 having a small diameter extending downward from the bottom of the columnar pores 12 are further formed.

The anodizing in the step (e) may be performed under the same conditions as in the step (a). The longer the anodizing time, the deeper the pores can be obtained.

(Step (f))
Step (f) is a step of repeating step (d) and step (e) to obtain a mold having anodized porous alumina having a plurality of pores on the surface. As shown in FIG. 1, it has pores 12 having a shape in which the diameter continuously decreases in the depth direction from the opening when the pore diameter enlargement treatment in the step (d) and the anodizing in the step (e) are repeated. An oxide film 14 is formed, and a mold 18 having anodized porous alumina (a porous oxide film (anodized) of aluminum) on the surface of the aluminum base material 10 is obtained.

The number of repetitions is preferably 3 times or more, and more preferably 5 times or more, because pores whose diameters are continuously reduced can be obtained and the obtained film having an uneven structure on the surface is excellent in antireflection performance.
Since the end of the step (f) is excellent in smoothness of the inner wall of the pores, it is preferable to end with the pore diameter enlargement treatment of the step (d).

Examples of the shape of the pores include a substantially conical shape, a pyramidal shape, a bell shape, a cylindrical shape, and the like. Among these pore shapes, the pores in the direction orthogonal to the depth direction, such as conical shape, pyramid shape, bell shape, etc., are excellent in antireflection performance of the film having the obtained uneven structure on the surface. A shape in which the cross-sectional area continuously decreases in the depth direction from the outermost surface is preferable, and a conical shape, a pyramid shape, and a bell shape are more preferable.

The average spacing between adjacent pores is preferably equal to or less than the wavelength of visible light, that is, 400 nm or less, and more preferably 380 nm or less, because the film having the obtained uneven structure on the surface is excellent in antireflection performance.

The average spacing between adjacent pores is preferably 20 nm to 300 nm, more preferably 80 nm to 200 nm. When the average spacing between adjacent pores is 20 nm or more, the convex portions are likely to be formed when the pores are transferred to form the convex portions. Further, when the average spacing between adjacent pores is 300 nm or less, the voltage for increasing the pore spacing can be suppressed, and it is easy to industrially produce anodized porous alumina.

In the present specification, the average spacing between adjacent pores is the spacing between adjacent pores (distance from the center of the pores to the center of the adjacent pores) at random 10 using electron microscopy. Point measurement is performed and these values are averaged.

The average depth of the pores is preferably 60 nm to 400 nm, more preferably 90 nm to 350 nm. When the average depth of the pores is 60 nm or more, it is possible to suppress an increase in the minimum reflectance and the reflectance at a specific wavelength, and the film having the obtained uneven structure on the surface is excellent in antireflection performance. Further, when the average depth of the pores is 400 nm or less, the pores are easily formed, and the film having the obtained uneven structure on the surface is excellent in scratch resistance.

In the present specification, the average depth of pores is measured at 10 points at random, using electron microscopic observation, to measure the vertical distance between the bottom of the pores and the top of the convex portion existing between the pores. Then, let these values be the average value.

The aspect ratio of the pores (average depth of pores / average spacing between adjacent pores) is preferably 0.8 to 5.0, more preferably 1.2 to 4.0, and 1.5 to 3 .0 is more preferred. When the aspect ratio of the pores is 0.8 or more, the antireflection performance of the film having the obtained uneven structure on the surface is excellent. Further, when the aspect ratio of the pores is 5.0 or less, the pores are easily formed, and the film having the obtained uneven structure on the surface is excellent in scratch resistance.

(Film manufacturing method)
Since the method for producing a film of the present invention is excellent in productivity, it is preferable to sequentially include the following steps (1) to (3).
Step (1): A step of applying the mold release treatment solution of the present invention to the mold surface.
Step (2): A step of supplying the curable composition to the surface of the mold and curing the curable composition.
Step (3): A step of peeling the cured product from the mold.

(Step (1))
The step (1) is a step of applying the mold release treatment solution of the present invention to the mold surface. By applying the mold release treatment solution of the present invention to the mold surface and drying it, the solvent (B) is volatilized and a layer of the (poly) oxyalkylene alkyl phosphoric acid compound (A) is formed on the mold surface. To.

Examples of the coating method include dip coating, spray coating, flushing, and wiping with a wiper. Among these coating methods, spray coating and flushing are preferable because they are excellent in coating uniformity.

Examples of the drying method include standing in a clean environment, drying in a high-temperature dryer, vacuum drying, drying by gas spraying, and the like. Among these drying methods, drying by gas spraying is preferable because the coating uniformity is excellent.

The thickness of the layer of the (poly) oxyalkylene alkyl phosphoric acid compound (A) is preferably 1 nm to 100 nm, more preferably 2 nm to 50 nm. When the thickness of the layer of the (poly) oxyalkylene alkyl phosphoric acid compound (A) is 1 nm or more, the releasability can be sufficiently ensured. Further, when the thickness of the layer of the (poly) oxyalkylene alkyl phosphoric acid compound (A) is 100 nm or less, the quality stability of the film having the obtained uneven structure on the surface is excellent.

(Step (2))
The step (2) is a step of supplying the curable composition to the surface of the mold and curing the curable composition. In step (2), since the film having an uneven structure on the surface is excellent in productivity, a curable composition that is cured by active energy rays is sandwiched between a mold and a base material, and active energy rays are applied thereto. It is preferable to irradiate and cure.

(Base material)
Examples of the material of the base material include acrylic resin such as polymethylmethacrylate; polycarbonate resin; styrene resin such as polystyrene and methylmethacrylate-styrene copolymer; cellulose resin such as cellulose diacetate, cellulose triacetate and cellulose acetate butyrate; Polyester resin such as polyethylene terephthalate; polyamide resin; polyimide resin; polyether sulphon resin; polysulphon resin; polyolefin resin such as polypropylene, polymethylpentene, alicyclic polyolefin; vinyl chloride resin such as polyvinyl chloride; polyvinyl acetal resin; Polyether ketone resin; polyurethane resin; glass and the like can be mentioned. Among these base material materials, acrylic resin, polycarbonate resin, polyester resin, and cellulose resin are preferable, and polyester resin and cellulose resin are more preferable, because they are excellent in light transmission and handleability.

Examples of the form of the base material include known forms such as films and sheets. Among these forms of the base material, films and sheets are preferable because they are excellent in productivity and handleability of films having an uneven structure on the surface.

Examples of the method for manufacturing the base material include known manufacturing methods such as an injection molding method, an extrusion molding method, and a cast molding method. Among these methods for producing a base material, an extrusion molding method and a cast molding method are preferable because they are excellent in productivity.

The surface of the base material may be coated, corona-treated, or the like for the purpose of improving properties such as adhesion, antistatic property, scratch resistance, and weather resistance.

The difference in refractive index between the cured product of the curable composition and the substrate can suppress the reflection of light at the interface between the layer of the cured product of the curable composition and the substrate, and the optical performance such as antireflection performance. 0.3 or less is preferable, and 0.1 or less is more preferable.

(Curable composition)
As the curable composition, a composition that is cured by active energy rays is preferable because it is excellent in productivity of a film having a concavo-convex structure on the surface.
Examples of the active energy ray include visible light, ultraviolet light, electron beam, plasma, heat ray (infrared ray, etc.) and the like. Among these active energy rays, ultraviolet rays and electron beams are preferable, and ultraviolet rays are more preferable, because the curable composition is excellent in curability.

The curable composition preferably contains a polymerizable compound, a polymerization initiator, and, if necessary, other additives.

(Polymerizable compound)
Examples of the polymerizable compound include a monomer containing at least one of a radically polymerizable bond and a cationically polymerizable bond in the molecule, an oligomer, a reactive polymer and the like. These polymerizable compounds may be used alone or in combination of two or more.

Examples of the monomer having a radically polymerizable bond include a monofunctional monomer and a polyfunctional monomer.

Examples of the monofunctional monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and s-butyl (meth) acrylate. t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, alkyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate , 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate and other (meth) acrylate derivatives; (meth) acrylic acid; (meth) acrylonitrile; styrene, α-methylstyrene and other styrene derivatives; (meth) ) Examples thereof include (meth) acrylamide derivatives such as acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and dimethylaminopropyl (meth) acrylamide. These monofunctional monomers may be used alone or in combination of two or more. Among these monofunctional monomers, alkyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, and 2-hydroxyethyl (meth) acrylate are preferable because of their excellent curability, and alkyl acrylate, N, N-dimethyl. Acrylamide and 2-hydroxyethyl acrylate are more preferable.
As used herein, (meth) acrylic refers to acrylic, methacrylic, or both.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, isocyanurate ethylene oxide-modified di (meth) acrylate, and trimethylolpropane di (meth) acrylate. Meta) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,3-butylene glycol Di (meth) acrylate, polybutylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) Propane, 2,2-bis (4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl) propane, 1,2-bis (3- (meth) acryloxy-2-hydroxypropoxy) ethane, 1,4 -Bis (3- (meth) acryloxy-2-hydroxypropoxy) butane, dimethyloltricyclodecanedi (meth) acrylate, ethylene oxide adduct di (meth) acrylate of bisphenol A, propylene oxide adduct di (meth) acrylate of bisphenol A ( Bifunctional monomers such as meth) acrylate, neopentyl glycol di (meth) acrylate, divinylbenzene, methylenebisacrylamide; pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene Trifunctional monomers such as oxide-modified tri (meth) acrylate, trimethylolpropane propylene oxide-modified triacrylate, trimethylolpropane ethylene oxide-modified triacrylate, and isocyanurate ethylene oxide-modified tri (meth) acrylate; succinic acid / trimethylolethane / acrylic. Acid condensation reaction mixture, pentaerythritol tetra (meth) acrylate, dipentaeristolhexa (meth) acrylate, dipentaeristolpenta (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra Four functionalities such as acrylate, tetramethylolmethanetetra (meth) acrylate, etc. The above monomer; a bifunctional or higher urethane acrylate, a bifunctional or higher polyester acrylate, and the like can be mentioned. These polyfunctional monomers may be used alone or in combination of two or more. Among these polyfunctional monomers, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and ethylene are excellent in durability. Oxide-modified dipentaerythritol hexa (meth) acrylate and polyethylene glycol di (meth) acrylate are preferable, and pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ethylene oxide-modified dipentaerythritol hexa. Acrylate and polyethylene glycol diacrylate are more preferable.

Examples of the monomer having a cationically polymerizable bond include a monomer having an epoxy group, an oxetanyl group, an oxazolyl group, a vinyloxy group and the like. As these monomers having a cationically polymerizable bond, one type may be used alone, or two or more types may be used in combination. Among these monomers having a cationically polymerizable bond, a monomer having an epoxy group is preferable because it has excellent durability.

Specific examples of the monomer having a cationically polymerizable bond include, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. , Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A polypropylene oxide 2 mol adduct diglycidyl ether, 3-Ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, xylylenebis oxetane, 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane, 2-hydroxyethylvinyl ether, 4 -Hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, 2-ethylhexyl vinyl ether and the like can be mentioned. As these monomers having a cationically polymerizable bond, one type may be used alone, or two or more types may be used in combination. Among these monomers having a cationically polymerizable bond, diethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether are preferable because they are excellent in durability.

Examples of the oligomer or the reactive polymer include unsaturated polyesters such as a condensate of an unsaturated dicarboxylic acid and a polyhydric alcohol; polyester (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, and epoxy ( Examples thereof include meta) acrylate, urethane (meth) acrylate, cationically polymerizable epoxy compound, and the above-mentioned monomer alone or copolymerized polymer having a radically polymerizable group in the side chain. These oligomers or reactive polymers may be used alone or in combination of two or more. Among these oligomers or reactive polymers, epoxy (meth) acrylate and urethane (meth) acrylate are preferable, and urethane (meth) acrylate is more preferable because they are excellent in scratch resistance.

Since the combination of the polymerizable compounds is excellent in reactivity and curability, a combination of monomers having a radically polymerizable bond and a combination of a monomer having a radically polymerizable bond and a monomer having a cationically polymerizable bond are preferable, and radicals are preferable. A combination of monomers having a polymerizable bond is more preferable.

(Polymer initiator)
When a photocuring reaction is used for curing the curable composition, it is preferable to use a photopolymerization initiator as the polymerization initiator.
Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl, benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone, α, α-dimethoxy-. α-Phenylacetophenone, Methylphenylglycolate, Ethylphenylglycolate, 4,4'-bis (dimethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy- Carbonyl compounds such as cyclohexylphenyl ketone; sulfur compounds such as tetramethylthium monosulfide and tetramethylthium disulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphos Examples thereof include acylphosphine oxides such as fin oxide. These photopolymerization initiators may be used alone or in combination of two or more. Among these photopolymerization initiators, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,4,6-trimethyl are excellent in curability. Benzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphin oxide is preferred, 1-hydroxy-cyclohexyl-phenyl-ketone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine. Oxides are more preferred.

When a thermosetting reaction is used for curing the curable composition, it is preferable to use a thermosetting initiator as the polymerization initiator.
Examples of the thermal polymerization initiator include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctate, t-butyl peroxybenzoate, and lauroyl. Organic peroxides such as peroxide; azo compounds such as azobisisobutyronitrile; Redox in which the organic peroxide is combined with amines such as N, N-dimethylaniline and N, N-dimethyl-p-toluidine. Examples thereof include a polymerization initiator. These thermal polymerization initiators may be used alone or in combination of two or more. Among these thermal polymerization initiators, organic peroxides and azo compounds are preferable, and azo compounds are more preferable, because they are excellent in reactivity and curability.

The content of the polymerization initiator is preferably 0.1 part by mass to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound. When the content of the polymerization initiator is 0.1 parts by mass or more, the polymerization is likely to proceed. Further, when the content of the polymerization initiator is 10% by mass or less, the mechanical strength of the cured product is excellent and the coloring of the cured product can be suppressed.

(Other additives)
The curable composition may contain other additives, if necessary, in addition to the polymerizable compound and the polymerization initiator.
Other additives include, for example, mold release agents, non-reactive polymers, active energy ray solgel-reactive compositions, antistatic agents, additives such as fluorine compounds for improving antifouling properties, fine particles, and small amounts. Examples include a solvent. These other additives may be used alone or in combination of two or more.

(Release agent)
The curable composition preferably contains a release agent because it can improve continuous transferability.
The mold release agent improves the mold release property between the cured product of the curable composition and the surface of the mold, and is not particularly limited as long as it is compatible with the curable composition.

Examples of the mold release agent include (poly) oxyalkylene alkyl phosphoric acid compounds, phosphoric acid ester-based compounds, fluorine-containing compounds, silicone-based compounds, compounds having a long-chain alkyl group, and solid waxes (polyalkylene wax, amide wax, etc.). Teflon (trade name) powder, etc.) and the like. These release agents may be used alone or in combination of two or more. Among these mold release agents, a (poly) oxyalkylene alkyl phosphoric acid compound is preferable and is used as a mold release treatment solution because it is excellent in mold release property between the cured product of the curable composition and the mold surface (poly) oxyalkylene alkyl phosphate (poly). The same compound as the poly) oxyalkylene alkyl phosphate compound (A) is more preferable.

By making the mold release agent in the curable composition and the (poly) oxyalkylene alkyl phosphoric acid compound (A) used in the mold release treatment solution the same compound, the mold release property between the cured product and the mold can be obtained. Excellent. Further, since the load at the time of mold release is extremely low, the uneven structure is less likely to be damaged, and the uneven structure of the mold can be transferred efficiently and accurately.

The difference in SP value between the mold release agent in the curable composition and the (poly) oxyalkylene alkyl phosphate compound (A) used in the mold release treatment solution causes whitening of the film having the obtained uneven structure on the surface. Since it can be suppressed, 2.0 or less is preferable, and 1.0 or less is more preferable.

In the present specification, the SP value is a solubility parameter ((J / cm ³ ) ^1/2 ) calculated by the Fedors method, and is a value represented by the following formula (2).
SP value (δ) = (ΔH / V) ^1/2 ... (2)
In the formula, ΔH represents the molar heat of vaporization (J) and V represents the molar volume (cm ³ ). ΔH and V are the total molar heats of vaporization (Δei) of the atomic group described in "POLYMER ENGINEERING AND SCIENCE, 1974, Vol. 14, No. 2, ROBERT F. FEDORS (pages 151 to 153)", respectively. The total ΣΔvi (= V) of ΣΔei (= ΔH) and molar volume (Δvi) can be used, and the SP value is calculated from (ΣΔei / ΣΔvi) ^1/2 .

The content of the release agent in the curable composition is preferably 0.01 part by mass to 1 part by mass, more preferably 0.05 part by mass to 0.5 part by mass with respect to 100 parts by mass of the polymerizable compound. , 0.05 part by mass to 0.1 part by mass is more preferable. When the content of the mold release agent in the curable composition is 0.01 parts by mass or more, the mold release property between the cured product and the mold is excellent. Further, when the amount is 1 part by mass or less, deterioration of the performance of the film having the obtained uneven structure on the surface can be suppressed.

(Non-reactive polymer)
The curable composition preferably contains a non-reactive polymer because of its excellent durability.
Examples of the non-reactive polymer include acrylic resin, styrene resin, polyurethane, cellulosic resin, polyvinyl butyral, polyester, thermoplastic elastomer and the like. These non-reactive polymers may be used alone or in combination of two or more. Among these non-reactive polymers, acrylic resins are preferable.

(Active energy ray sol-gel reactive composition)
Since the curable composition is excellent in durability, it is preferable to include an active energy ray sol-gel reactive composition.
Examples of the active energy ray sol-gel reactive composition include an alkoxysilane compound and an alkyl silicate compound. These active energy ray sol-gel reactive compositions may be used alone or in combination of two or more. Among these active energy ray sol-gel reactive compositions, an alkoxysilane compound is preferable.

Examples of the alkoxysilane compound include tetramethoxysilane, tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-t-butoxysilane, and methyltriethoxy. Examples thereof include silane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, trimethylpropoxysilane, and trimethylbutoxysilane. One of these alkoxysilane compounds may be used alone, or two or more thereof may be used in combination. Among these alkoxysilane compounds, tetramethoxysilane and trimethylmethoxysilane are preferable.

Examples of the alkyl silicate compound include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, n-butyl silicate, n-pentyl silicate, and acetyl silicate. These alkyl silicate compounds may be used alone or in combination of two or more. Among these alkyl silicate compounds, methyl silicate and ethyl silicate are preferable.

A film having an uneven structure on its surface is superhydrophobic if its surface is formed of a hydrophobic material due to the Lotus effect, and is superhydrophilic if its surface is formed of a hydrophilic material. can get.

(Hydrophobic material)
When water repellency is imparted to the surface of a film having an uneven structure on the surface (specifically, the contact angle between the uneven structure and water is 90 ° or more), the surface is formed of a hydrophobic material.
As the raw material of the hydrophobic material, a fluorine-containing compound and a silicone-based compound are preferable because they can suppress the adhesion of stains such as fingerprints.

Examples of the fluorine-containing compound include a fluorine-containing monomer, a fluorine-containing silane compound, a fluorine-containing surfactant, and a fluorine-containing polymer. These fluorine-containing compounds may be used alone or in combination of two or more.

Examples of the fluorine-containing monomer include a fluoroalkyl group-substituted vinyl monomer and a fluoroalkyl group-substituted ring-opening polymerizable monomer. These fluorine-containing monomers may be used alone or in combination of two or more.

Examples of the fluoroalkyl group-substituted vinyl monomer include a fluoroalkyl group-substituted (meth) acrylate, a fluoroalkyl group-substituted (meth) acrylamide, a fluoroalkyl group-substituted vinyl ether, and a fluoroalkyl group-substituted styrene. These fluoroalkyl group-substituted vinyl monomers may be used alone or in combination of two or more.

Examples of the fluoroalkyl group-substituted ring-opening polymerizable monomer include a fluoroalkyl group-substituted epoxy compound, a fluoroalkyl group-substituted oxetane compound, and a fluoroalkyl group-substituted oxazoline compound. As the fluoroalkyl group-substituted ring-opening polymerizable monomer, one type may be used alone, or two or more types may be used in combination.

Examples of the fluorine-containing silane compound include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriacetoxysilane, dimethyl-3,3,3-trifluoropropylmethoxysilane, and tri. Examples thereof include decafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane. These fluorine-containing silane compounds may be used alone or in combination of two or more.

Examples of the fluorine-containing surfactant include a fluoroalkyl group-containing anionic surfactant and a fluoroalkyl group-containing cationic surfactant. These fluorine-containing surfactants may be used alone or in combination of two or more.

Examples of the fluorine-containing polymer include a polymer of a fluoroalkyl group-containing monomer, a copolymer of a fluoroalkyl group-containing monomer and a poly (oxyalkylene) group-containing monomer, and a fluoroalkyl group-containing monomer and a cross-linking reactive group-containing monomer. Examples thereof include the copolymer of the above. The fluoropolymer may be a copolymer with another copolymerizable monomer. These fluoropolymers may be used alone or in combination of two or more.

Examples of the silicone-based compound include (meth) acrylic acid-modified silicone, a silicone resin, and a silicone-based silane coupling agent. These silicone compounds may be used alone or in combination of two or more.

Examples of the (meth) acrylic acid-modified silicone include silicone (di) (meth) acrylate and the like. These (meth) acrylic acid-modified silicones may be used alone or in combination of two or more.
As the (meth) acrylic acid-modified silicone, a commercially available product may be used. Commercially available products of (meth) acrylic acid-modified silicone include, for example, X-22-164 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and X-22-1602 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). And so on.

(Hydrophilic material)
When imparting hydrophilicity to the surface of a film having a concavo-convex structure on its surface (specifically, the contact angle between the concavo-convex structure and water is 25 ° or less), the surface is formed of a hydrophilic material.
Since the raw material of the hydrophilic material can easily remove stains such as fingerprints by wiping with water, it is preferable to contain at least a hydrophilic monomer, and since it is excellent in scratch resistance and water resistance, it can be further crosslinked. It is more preferable to contain a polyfunctional monomer. The hydrophilic monomer and the crosslinkable polyfunctional monomer may be the same or different.
Specifically, since the raw material of the hydrophilic material can easily remove stains such as fingerprints by wiping with water, it is a polyfunctional (meth) acrylate having four or more functionalities and a hydrophilic (meth) having two or more functionalities. It preferably contains an acrylate and, if necessary, a monofunctional monomer.

Examples of the polyfunctional (meth) acrylate having four or more functions include ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, and dipentaerythritol hydroxypenta (meth) acrylate. , Dipentaerythritol hexa (meth) acrylate, condensation reaction mixture of succinic acid / trimethylolethane / acrylic acid in molar ratio 1: 2: 4, urethane acrylates (specifically, for example, manufactured by Daicel Ornex Co., Ltd.). EBECRYL220, EBECRYL1290, EBECRYL1290K, EBECRYL5129, EBECRYL8210, EBECRYL8301, KRM8200 (trade name), etc.) Epoxy acrylates (specifically, for example, EBECRYL3416 (trade name) manufactured by Daicel Ornex Co., Ltd.), polyester acrylates (specifically, for example, EBECRYL450, EBECRYL657 manufactured by Daicel Ornex Co., Ltd.), EBECRYL800, EBECRYL810, EBECRYL811, EBECRYL812, EBECRYL1830, EBECRYL845, EBECRYL846, EBECRYL1870 (trade name), etc.) and the like. These four or more functional polyfunctional (meth) acrylates may be used alone or in combination of two or more. Among these tetrafunctional (meth) acrylates having four or more functionalities, polyfunctional (meth) acrylates having five or more functionalities are preferable because they are excellent in durability.

The content of the polyfunctional (meth) acrylate having four or more functionalities is preferably 40% by mass to 90% by mass, more preferably 50% by mass to 85% by mass, and 60% by mass to 80% by mass in 100% by mass of the polymerizable compound. % Is more preferable. When the content of the polyfunctional (meth) acrylate having four or more functionalities is 40% by mass or more, the elastic modulus is improved and the scratch resistance is excellent. Further, when the content of the polyfunctional (meth) acrylate having four or more functionalities is 90% by mass or less, the surface is less likely to be cracked and the surface appearance is excellent.

Examples of the bifunctional or higher hydrophilic (meth) acrylate include polyfunctional acrylate having polyethylene glycol, polyethylene glycol dimethacrylate and the like. These bifunctional or higher functional hydrophilic (meth) acrylates may be used alone or in combination of two or more.

As the polyfunctional acrylate having polyethylene glycol, a commercially available product may be used. Commercially available products of polyfunctional acrylate having polyethylene glycol include, for example, Aronix M-240 (trade name, manufactured by Toa Synthetic Co., Ltd.), Aronix M-260 (trade name, manufactured by Toa Synthetic Co., Ltd.), NK Ester AT. -20E (trade name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), NK ester ATM-35E (trade name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and the like can be mentioned.

The total average repeating unit of the polyethylene glycol chain present in one molecule of the polyethylene glycol di (meth) acrylate is preferably 6 to 40, more preferably 9 to 30, and even more preferably 12 to 20. When the total average repeating unit of the polyethylene glycol chain existing in one molecule of the polyethylene glycol di (meth) acrylate is 6 or more, the hydrophilicity is excellent and the antifouling property is improved. Further, when the total average repeating unit of the polyethylene glycol chain existing in one molecule of the polyethylene glycol di (meth) acrylate is 40 or less, the compatibility with the polyfunctional (meth) acrylate having four or more functions is excellent.

The content of the bifunctional or higher hydrophilic (meth) acrylate is preferably 10% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and 20% by mass to 40% by mass in 100% by mass of the polymerizable compound. % Is more preferable. When the content of the bifunctional or higher hydrophilic (meth) acrylate is 20% by mass or more, the hydrophilicity is excellent and the antifouling property is improved. Further, when the content of the hydrophilic (meth) acrylate having two or more functions is 80% by mass or less, the elastic modulus is improved and the scratch resistance is excellent.

As the monofunctional monomer, a hydrophilic monofunctional monomer is preferable because stains such as fingerprints can be easily removed by wiping with water.

Examples of the hydrophilic monofunctional monomer include monofunctional (meth) acrylate having a polyethylene glycol chain as an ester group, monofunctional (meth) acrylate having a hydroxyl group as an ester group such as hydroxyalkyl (meth) acrylate, and monofunctional acrylamides. , Cationic monomers such as methacrylamidopropyltrimethylammonium methylsulfate, methacryloyloxyethyltrimethylammonium methylsulfate and the like. These hydrophilic monofunctional monomers may be used alone or in combination of two or more.

As the monofunctional (meth) acrylate having a polyethylene glycol chain as an ester group, a commercially available product may be used. Commercially available products of monofunctional (meth) acrylate having a polyethylene glycol chain as an ester group include, for example, M-20G (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd.) and M-90G (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd.). (Manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), M-230G (trade name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and the like.

As the monofunctional monomer, a viscosity modifier such as acryloyl morpholine or vinylpyrrolidone, an adhesion improver such as acryloyl isocyanates for improving adhesion to a substrate, or the like may be used.

Since the content of the monofunctional monomer is excellent in hydrophilicity and scratch resistance, it is preferably 0% by mass to 20% by mass, more preferably 0% by mass to 15% by mass, and 0% by mass in 100% by mass of the polymerizable compound. % To 10% by mass is more preferable. When the content of the monofunctional monomer is 20% by mass or less, the hydrophilicity and scratch resistance are excellent.

The viscosity of the curable composition is preferably 10,000 mPa · s or less, more preferably 5000 mPa · s or less, still more preferably 2000 mPa · s or less, because it is excellent in following the curable composition to the uneven structure.
In the present specification, the viscosity of the curable composition is a value measured at 25 ° C. using a rotary E-type viscometer.

(Step (3))
The step (3) is a step of peeling the cured product from the mold.

(Film manufacturing equipment)
In the steps (1) to (3), it is preferable to use the manufacturing apparatus shown in FIG. 2 because the film having the uneven structure on the surface is excellent in productivity.
FIG. 2 is a schematic cross-sectional view showing a film manufacturing apparatus having an uneven structure on the surface. Hereinafter, a method for manufacturing a film having a concavo-convex structure on the surface will be described with reference to FIG. 2, but the method for manufacturing a film having a concavo-convex structure on the surface is not limited to FIG.

The method for manufacturing a film having an uneven structure on the surface using the manufacturing apparatus shown in FIG. 2 is as follows.
A roll-shaped mold 20 having an inverted structure having an uneven structure on its surface and a strip-shaped base material 42 that moves along the surface of the roll-shaped mold 20 in synchronization with the rotation of the roll-shaped mold 20. In the meantime, the curable composition 38 is supplied from the tank 22. The base material 42 and the curable composition 38 are nipped between the roll-shaped mold 20 and the nip roll 26 whose nip pressure is adjusted by the pneumatic cylinder 24, and the curable composition 38 is combined with the base material 42. At the same time as being evenly distributed between the roll-shaped mold 20 and the roll-shaped mold 20, the recesses of the roll-shaped mold 20 are filled. By irradiating the curable resin composition 38 with active energy rays from the active energy ray irradiating device 28 installed on the outside of the roll-shaped mold 20 through the base material 42 and curing the curable resin composition 38, the curable resin composition 38 is cured. The cured resin layer 44 to which the uneven structure on the surface of the roll-shaped mold 20 is transferred is formed.
By peeling the base material 42 having the cured resin layer 44 formed on the surface from the roll-shaped mold 20 by the peeling roll 30, the film 40 having the uneven structure on the surface can be obtained.

Examples of the active energy ray irradiation device include chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, electrodeless ultraviolet lamps, visible light halogen lamps, xenon lamps, and ultraviolet LEDs. Among these active energy ray irradiation devices, electrodeless ultraviolet lamps and ultraviolet LEDs are preferable because heat generation can be suppressed.

The amount of light irradiation energy is preferably 100 mJ / cm ² to 10000 mJ / cm ² , more preferably 200 mJ / cm ² to 5000 mJ / cm ² . When the amount of light irradiation energy is 100 mJ / cm ² or more, the curable composition is excellent in curability. Further, when the amount of light irradiation energy is 10,000 mJ / cm ² or less, coloring of the cured product can be suppressed.

(the film)
By the method for producing a film of the present invention, for example, a film having an uneven structure shown in FIG. 3 on its surface can be obtained. Hereinafter, a film having an uneven structure on the surface obtained by the method for producing a film of the present invention will be described with reference to FIG. 3, but a film having an uneven structure on the surface obtained by the method for producing a film of the present invention is shown in FIG. Not limited to.

FIG. 3 is a schematic cross-sectional view showing an example of a film having an uneven structure on its surface. The film 40 having the uneven structure shown in FIG. 3 on the surface has a cured resin layer 44 on the base material 42, and the cured resin layer 44 has a plurality of convex portions 46.

Examples of the uneven structure include a prism structure, a microlens structure, a moth-eye structure, and the like. Among these uneven structures, the moth-eye structure is preferable because the effect of the present invention is more required.

Examples of the shape of the convex portion include a substantially conical shape, a pyramid shape, a bell shape, a cylindrical shape, and the like. Among these convex shapes, the convex portions in the direction orthogonal to the height direction, such as a conical shape, a pyramid shape, and a bell shape, are excellent in antireflection performance of the film having the obtained uneven structure on the surface. A shape in which the cross-sectional area continuously increases in the depth direction from the top is preferable, and a conical shape, a pyramid shape, and a bell shape are more preferable.
The convex portion may be one in which a plurality of fine convex portions are united to form one convex portion.

The average spacing between adjacent convex portions is preferably equal to or less than the wavelength of visible light, that is, 400 nm or less, and more preferably 380 nm or less, because the film having the obtained uneven structure on the surface is excellent in antireflection performance.

The average spacing between adjacent protrusions is preferably 20 nm to 300 nm, more preferably 80 nm to 200 nm. When the average spacing between adjacent convex portions is 20 nm or more, the convex portions are likely to be formed when the pores are transferred to form the convex portions. Further, when the average spacing between adjacent convex portions is 300 nm or less, the voltage for increasing the pore spacing can be suppressed, and it is easy to industrially produce anodized porous alumina.

In the present specification, the average spacing between adjacent convex portions is the interval between adjacent convex portions (distance from the center of the convex portion to the center of the adjacent convex portion) at random 10 using electron microscope observation. Point measurement is performed and these values are averaged.

The average height of the convex portion is preferably 60 nm to 400 nm, more preferably 90 nm to 350 nm. When the average height of the convex portion is 60 nm or more, it is possible to suppress an increase in the minimum reflectance and the reflectance at a specific wavelength, and the film having the obtained uneven structure on the surface is excellent in antireflection performance. Further, when the average height of the convex portion is 400 nm or less, pores are easily formed, and the film having the obtained uneven structure on the surface is excellent in scratch resistance.

In the present specification, the average height of the convex portion is measured by randomly measuring 10 points of the vertical distance between the top of the convex portion and the bottom of the concave portion existing between the convex portions by using electron microscope observation. , These values are averaged.

The aspect ratio of the convex portions (average height of the convex portions / average spacing between adjacent convex portions) is preferably 0.8 to 5.0, more preferably 1.2 to 4.0, and 1.5 to 3 .0 is more preferred. When the aspect ratio of the convex portion is 0.8 or more, the antireflection performance of the film having the obtained uneven structure on the surface is excellent. Further, when the aspect ratio of the convex portion is 5.0 or less, pores are easily formed, and the film having the obtained uneven structure on the surface is excellent in scratch resistance.

When water repellency is imparted to the surface of a film having an uneven structure on the surface, the contact angle between the uneven structure and water is preferably 90 ° or more because water stains are less likely to adhere and icing can be suppressed. 110 ° or more is more preferable, and 120 ° or more is further preferable.

When imparting hydrophilicity to the surface of a film having an uneven structure on the surface, the contact angle between the uneven structure and water is preferably 25 ° or less, preferably 23 ° or less, because it can be washed with water and oil stains do not easily adhere to it. More preferably, 21 ° or more is further preferable. Further, when hydrophilicity is imparted to the surface of a film having a concavo-convex structure on the surface, the contact angle between the concavo-convex structure and water can be 3 ° or more because deformation of the concavo-convex structure and an increase in reflectance can be suppressed. preferable.

(Use)
Applications of the film having an uneven structure on the surface include, for example, antireflection articles, antifogging articles, antifouling articles, water repellent articles, more specifically, antireflection for displays, clock dials, touch panel members, and the like. Examples thereof include a dirt adsorbing member, a humidity control member, an antibacterial member, a sanitary member, an automobile meter cover, an automobile mirror, an automobile window, an organic or inorganic electroluminescence light extraction efficiency improving member, and a solar cell member.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

(material)
(Poly) Oxyalkylene alkyl phosphoric acid compound (A-1): TDP-2 (trade name, manufactured by Nikko Chemicals Co., Ltd., R ¹ : alkyl group having 12 to 15 carbon atoms, R ² : ethylene group, m≈2 , N≈3)
(Poly) Oxyalkylene alkyl phosphoric acid compound (A-2): TDP-8 (trade name, manufactured by Nikko Chemicals Co., Ltd., R ¹ : alkyl group having 12 to 15 carbon atoms, R ² : ethylene group, m≈8 , N≈3)
Solvent (B-1): 1-propanol Solvent (B-2): Ethylene glycol Solvent (B-3): Isopropanol Solvent (B-4): Diethylene glycol monomethyl ether solvent (B-5): N-methyl-2- Pyrrolidone solvent (B-6): acetone solvent (B-7): water

(Solubility test)
The mold release treatment solutions obtained in Examples and Comparative Examples were visually observed and evaluated according to the following evaluation criteria.
A: It was colorless and transparent.
B: Slightly cloudy, but no precipitate was confirmed.
C: It became cloudy and a precipitate was confirmed.

(Fingerprint stain removal test)
The fingerprint is attached to the mold obtained in the production example, and the mold having the fingerprint attached to the mold release treatment solution obtained in the examples and comparative examples is immersed at 23 ° C. for 30 minutes, and then the mold is used. Was taken out and dried at 23 ° C. for 24 hours. The state of fingerprint stains before and after immersion was visually observed and evaluated according to the following evaluation criteria.
A: Fingerprint stains were almost completely removed.
B: Most of the fingerprint stains were removed.
C: Fingerprint stains were hardly removed.

(Wetability test with mold)
The mold release treatment solution obtained in Examples and Comparative Examples was dropped onto the surface of the mold obtained in the production example with a 10 μl syringe, and evaluated according to the following evaluation criteria.
A: It got wet and spread.
B: Slightly wet and spread.
C: It hardly got wet and spread.

(Coating uniformity test)
The mold release treatment solution obtained in Examples and Comparative Examples was poured onto the surface of the mold obtained in the production example with a dropper, the mold was tilted at 45 °, and dried at 23 ° C for 24 hours. The uneven drying of the mold release treatment solution after drying was visually observed and evaluated according to the following evaluation criteria.
A: It was applied evenly and there was no uneven drying.
B: There was slight unevenness in drying.
C: There was uneven drying in many places.

(Presence or absence of mold)
The mold release treatment solutions obtained in Examples and Comparative Examples were stored at 23 ° C. for 10 days, and then the wall surface of the container was visually observed and evaluated according to the following evaluation criteria.
◯: No mold was found.
×: Mold was confirmed to occur.

[Production example] Mold production A disk-shaped aluminum plate with a purity of 99.99% and a diameter of 70 mm is subjected to feather cloth polishing treatment, and then electrolytically polished in a perchloric acid / ethanol mixed solution (volume ratio = 1/4). , Mirrored.
The obtained aluminum substrate was anodized in a 0.3 M aqueous oxalic acid solution at a direct current of 40 V and a temperature of 16 ° C. for 30 minutes. Then, the aluminum substrate was immersed in a 6 mass% phosphoric acid / 1.8 mass% chromic acid mixed aqueous solution for 6 hours to remove the oxide film.
The obtained aluminum substrate was anodized in a 0.3 M aqueous oxalic acid solution at a direct current of 40 V and a temperature of 16 ° C. for 30 seconds.
The aluminum base material on which the obtained oxide film was formed was immersed in a 5% by mass phosphoric acid aqueous solution at 32 ° C. for 8 minutes to perform a pore size enlargement treatment (pore size enlargement treatment step). Then, the aluminum substrate was anodized in a 0.3 M aqueous oxalic acid solution at a direct current of 40 V and a temperature of 16 ° C. for 30 seconds (oxide film growth step). This pore size expansion treatment step and oxide film growth treatment step are repeated a total of four times, and finally the pore size expansion treatment step is performed to obtain anodized alumina having substantially conical pores with an average spacing of 100 nm and a depth of 200 nm. A disk-shaped mold formed on the surface was obtained.

[Example 1]
(Poly) Oxyalkylene alkyl phosphate compound (A-1) (TDP-2 (trade name), manufactured by Nikko Chemicals Co., Ltd., R ¹ : alkyl group having 12 to 15 carbon atoms, R ² : ethylene group, m≈ 2, n≈3)) 0.5 parts by mass is dissolved in a mixed solvent of 75 parts by mass of the solvent (B-1) (1-propanol) and 25 parts by mass of the solvent (B-7) (water), and gold is dissolved. A mold treatment solution was obtained.
The evaluation results of the obtained mold treatment solution are shown in Table 1.

[Examples 2 to 6]
The same procedure as in Example 1 was carried out except that the types and amounts of the (poly) oxyalkylene alkyl phosphoric acid compound (A) and the solvent (B) were changed as shown in Table 1, to obtain a mold treatment solution.
The evaluation results of the obtained mold treatment solution are shown in Table 1.

[Comparative Examples 1 to 4]
The same procedure as in Example 1 was carried out except that the types and amounts of the (poly) oxyalkylene alkyl phosphoric acid compound (A) and the solvent (B) were changed as shown in Table 1, to obtain a mold treatment solution.
The evaluation results of the obtained mold treatment solution are shown in Table 1.
The mold treatment solution obtained in Comparative Example 1 did not sufficiently dissolve the (poly) oxyalkylene alkyl phosphoric acid compound (A), and was subjected to a fingerprint stain removal test, a wettability test with a mold, and uniform coating. I gave up the sex test.

As can be seen from Table 1, the mold treatment solutions obtained in Examples 1 to 6 were excellent in solubility, fingerprint stain removing property, wettability with the mold, coating uniformity, and mold generation suppressing effect. Therefore, by using this mold treatment solution, it is expected that the mold releasability between the cured product and the mold is excellent, and the quality stability of the film having the uneven structure on the surface is excellent.
On the other hand, the mold treatment solutions obtained in Comparative Examples 1 to 4 were inferior in at least one performance of solubility, fingerprint stain removing property, wettability with a mold, and coating uniformity.

10 Aluminum base material 12 Pore 14 Oxidation film 16 Pore generation point 18 Mold with anodized porous alumina 20 Roll-shaped mold 22 Tank 24 Passivation cylinder 26 Nip roll 28 Active energy beam irradiation device 30 Peeling roll 38 Curable composition Object 40 Film with uneven structure on the surface 42 Base material 44 Cured resin layer 46 Convex part

Claims (10)

A mold release treatment solution containing the (poly) oxyalkylene alkyl phosphoric acid compound (A) and the solvent (B).
The solvent (B) contains an organic solvent and water, and the content of water in the solvent (B) is 5% by mass to 95.
By mass% ,
Mold release processing solution. The mold release treatment solution according to claim 1 , wherein the organic solvent is a water-soluble solvent. Claimed that the organic solvent is at least one selected from the group consisting of ethanol, 1-propanol, isopropanol, ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether and N-methyl-2-pyrrolidone. Item 2. The mold release treatment solution according to Item 2. The mold release treatment solution according to any one of claims 1 to 3 , wherein the (poly) oxyalkylene alkyl phosphoric acid compound (A) is a compound represented by the following formula (1).
(HO) _3-n (O =) P [-O- (R ² O) _m - R ¹ ] _n ... (1)
(In the formula, R ¹ is an alkyl group, R ² is an alkylene group, m is an integer of 1 to 20, and n is an integer of 1 to 3.) The mold release treatment solution according to claim 4 , wherein the (poly) oxyalkylene alkyl phosphoric acid compound (A) is (poly) oxyethylene alkyl ether phosphoric acid. The mold release treatment solution according to any one of claims 1 to 5 , wherein the mold is a mold for forming an uneven structure by transfer. The mold release treatment solution according to claim 6 , wherein the uneven structure is a moth-eye structure. A film manufacturing method comprising the following steps (1) to (3) in sequence.
Step (1): A step of applying the mold release treatment solution according to any one of claims 1 to 7 to the mold surface.
Step (2): A step of supplying the curable composition to the surface of the mold and curing the curable composition.
Step (3): A step of peeling the cured product from the mold. The film manufacturing method according to claim 8 , wherein the mold is a mold for forming an uneven structure by transfer. The film manufacturing method according to claim 9 , wherein the uneven structure is a moth-eye structure.

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