Laminate production method, film production method, film, support-provided film, and photosensitive transfer material

Abstract

The present invention pertains to: a laminate production method comprising a step for forming, on the surface of a support, a hydrophobic resin layer containing a hydrophobic resin, a step for forming a hydrophilic resin layer containing a hydrophilic resin on the surface of the hydrophobic resin layer, and a step for applying, on the surface of the hydrophilic resin layer, a composition containing an alcohol, and then drying the composition to form a protrusion structure on the hydrophilic resin layer-side surface of the hydrophobic resin layer and a recess structure on the hydrophobic resin layer-side surface of the hydrophilic resin layer; a film production method; a film; a support-provided film; and a photosensitive transfer material.

Description

Method for manufacturing laminate, method for manufacturing film, film, supported film, and photosensitive transfer material

[0001] The present disclosure relates to a method for producing a laminate, a method for producing a film, a film, a supported film, and a photosensitive transfer material.

[0002] Water-repellent films having at least one of a fine concave structure and a fine convex structure on the surface are produced by various methods, such as a method of stretching a film obtained by forming a composition containing a resin and particles into a film, or a method of pouring a composition containing a resin into a mold having at least one of a concave structure and a convex structure and curing the film.

[0003] However, in the method using a composition containing the above-mentioned resin and particles, the functionality of the produced water-repellent film, such as water repellency, may be insufficient.The method using a mold having at least one of a concave structure and a convex structure has problems such as a large number of steps and high production costs.

[0004] An object of an embodiment of the present disclosure is to provide a method for producing a laminate and a method for producing a film that are simple and capable of producing a film having excellent functionality.An object of an embodiment of the present disclosure is to provide a film, a supported film, and a photosensitive transfer material that can be produced by a simple method and have excellent functionality.

[0005] Specific means for solving the problems are as follows. <1> A method for producing a laminate, comprising the steps of: forming a hydrophobic resin layer containing a hydrophobic resin on the surface of a support; forming a hydrophilic resin layer containing a hydrophilic resin on the surface of the hydrophobic resin layer; and applying an alcohol-containing composition to the surface of the hydrophilic resin layer and drying it to form a convex structure on the surface of the hydrophobic resin layer facing the hydrophilic resin layer and a concave structure on the surface of the hydrophilic resin layer facing the hydrophobic resin layer. <2> A method for producing the laminate according to <1> above, wherein the support has a total light transmittance of 50% or more. <3> A method for producing the laminate according to <1> or <2> above, wherein the support contains a polyester resin. <4> A method for producing the laminate according to any one of <1> to <3> above, wherein the glass transition temperature of the hydrophobic resin is lower than the glass transition temperature of the hydrophilic resin. <5> A method for producing the laminate according to any one of <1> to <4> above, wherein the hydrophobic resin is a polyolefin resin. <6> The method for producing a laminate according to any one of <1> to <5> above, wherein the hydrophilic resin is a (meth)acrylic resin. <7> The method for producing a laminate according to any one of <1> to <6> above, wherein the composition further contains water. <8> A method for producing a film, comprising: producing a laminate by the method for producing a laminate according to <1> above, and peeling the hydrophobic resin layer and the hydrophilic resin layer provided in the laminate at an interface between them. <9> A film containing a hydrophobic resin, having, on at least one surface, a convex structure having a major axis of 0.02 μm to 5 μm and an average height of 10 nm to 3000 nm, ２<10> The film according to <9> above, wherein the surface on which the convex structure is formed has a water contact angle of 100° or more at 25°C. <11> The film according to <9> or <10> above, wherein the reflectance when the surface on which the convex structure is formed is irradiated with light with a wavelength of 550 nm is 4% or less. <12> A supported film comprising a support and the film according to any one of <9> to <11> above, provided on one surface of the support, wherein the surface of the film opposite the surface on which the convex structure is formed is in contact with the support. <13> The supported film according to <12> above, wherein the film is provided on both sides of the support, and wherein the transmittance of light with a wavelength of 550 nm is 92% or more. <14> A film containing a hydrophilic resin, having a concave structure having a major axis of 0.02 μm to 5 μm and an average depth of 10 nm to 3000 nm on at least one surface, and ２ <15> The film according to <14> above, wherein the surface on which the recessed structure is formed has a water contact angle of 95° or more at 25°C. <16> A film comprising a support, a hydrophobic resin layer, a hydrophilic resin layer, a water-soluble intermediate layer, and a photosensitive resin layer in this order, wherein the hydrophobic resin layer contains a polyolefin resin, the hydrophilic resin layer contains a (meth)acrylic resin, the water-soluble intermediate layer contains a water-soluble resin, the hydrophobic resin layer and the hydrophilic resin layer are peelable at the interface therebetween, and the hydrophilic resin layer has a 10 μm thick film on the surface on the hydrophobic resin layer side. ２ a photosensitive transfer material having 1 to 1000 recessed structures formed per surface, each recessed structure having a major axis of 0.02 μm to 5 μm and an average depth of 10 nm to 3000 nm, and a static friction coefficient of the surface against glass of 1.50 or less.

[0006] According to one embodiment of the present disclosure, it is possible to provide a laminate manufacturing method and a film manufacturing method that are simple and capable of manufacturing a film having excellent functionality. Furthermore, according to one embodiment of the present disclosure, it is possible to provide a film, a supported film, and a photosensitive transfer material that can be manufactured by a simple method and have excellent functionality.

[0007] FIG. 1 shows an SEM image (magnification 30,000x) of the surface of specific film A produced in Example 1-1 on which a convex structure is formed. FIG. 2 shows an SEM image (magnification 30,000x) of the surface of specific film B produced in Example 1-1 on which a concave structure is formed. FIG. 3 shows an SEM image (magnification 30,000x) of the surface of specific film A produced in Example 1-4 on which a convex structure is formed. FIG. 4 shows an SEM image (magnification 30,000x) of the surface of specific film B produced in Example 1-4 on which a concave structure is formed.

[0008] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. The present disclosure is not limited to the following embodiments and can be implemented with appropriate modifications within the scope of the object of the present disclosure. Components indicated by the same reference numerals in the drawings are the same components. Descriptions of duplicated components and reference numerals in the drawings may be omitted. The dimensional ratios in the drawings do not necessarily represent the actual dimensional ratios.

[0009] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the upper and lower limits. In the numerical ranges described in stages in the present disclosure, the upper or lower limit described in a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit described in a certain numerical range may be replaced with a value shown in the examples. In the present disclosure, the term "process" includes not only an independent process, but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. In the present disclosure, "(meth)acrylic" means both acrylic and methacrylic, or either one. In the present disclosure, when multiple substances corresponding to each component are present, the amount of each component in a composition, etc. means the total amount of the multiple substances present in the composition, etc., unless otherwise specified. In the present disclosure, a combination of two or more preferred embodiments or forms is a more preferred embodiment or form. In the present disclosure, "hydrophilic resin" means a resin having a polar group. In the present disclosure, the term "hydrophobic resin" refers to a resin that does not have a polar group. Examples of the polar group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphate group, an amide group, and an imide group. From the viewpoint of water repellency, a carboxyl group is preferred.

[0010] In the present disclosure, when an embodiment is described with reference to drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings.

[0011] [Method for manufacturing laminate] The method for manufacturing a laminate according to the present disclosure includes the steps of: forming a hydrophobic resin layer containing a hydrophobic resin on the surface of a support (hereinafter referred to as a step of forming a hydrophobic resin layer); forming a hydrophilic resin layer containing a hydrophilic resin on the surface of the hydrophobic resin layer (hereinafter referred to as a step of forming a hydrophilic resin layer); and applying a composition containing an alcohol (hereinafter referred to as a specific composition) to the surface of the hydrophilic resin layer, followed by drying, to form a convex structure on the hydrophilic resin layer side surface of the hydrophobic resin layer and a concave structure on the hydrophobic resin layer side surface of the hydrophilic resin layer (hereinafter referred to as a step of forming a convex structure and a concave structure).

[0012] The method for producing a laminate of the present disclosure may include a step of forming a photosensitive resin layer on the surface of the hydrophilic resin layer after applying and drying the specific composition. Furthermore, as described below, when a water-soluble intermediate layer is formed using the specific composition, the method for producing a laminate of the present disclosure may also include a step of forming a photosensitive resin layer on the surface of the water-soluble intermediate layer. Hereinafter, these two steps are collectively referred to as the step of forming a photosensitive resin layer.

[0013] (Step of forming hydrophobic resin layer) The method for producing a laminate of the present disclosure includes a step of forming a hydrophobic resin layer containing a hydrophobic resin on the surface of a support. The hydrophobic resin layer may contain two or more types of hydrophobic resin. It is preferable that the hydrophobic resin does not dissolve in water (25°C, pH 7) or methanol (25°C) at a concentration of 0.1 mass % or more.

[0014] Examples of hydrophobic resins include polyolefin resins, polystyrene resins, polyester resins, and (meth)acrylate resins. Among the above, from the viewpoints of water repellency, anti-reflection properties, etc., polyolefin resins are preferred, polyethylene, polypropylene, or ethylene vinyl acetate resins are more preferred, and polyethylene is even more preferred. Examples of polyethylene include high-density polyethylene resin (HDPE), medium-density polyethylene resin (MDPE), low-density polyethylene resin (LDPE), and linear low-density polyethylene resin (LLDPE), with LDPE or LLDPE being preferred. In the present disclosure, HDPE has a density of 0.945 g / cm ３ The density of the above polyethylene, MDPE, is 0.925 g / cm ３ 0.945g / cm or more ３ Polyethylene, LDPE and LLDPE have a density of less than 0.925 g / cm ３ This means polyethylene of less than

[0015] From the viewpoint of water repellency, anti-reflection properties, etc., the glass transition temperature (Tg) of the hydrophobic resin is preferably lower than the glass transition temperature of the hydrophilic resin contained in the hydrophilic resin layer, more preferably 50°C or more lower than the glass transition temperature of the hydrophilic resin contained in the hydrophilic resin layer, and more preferably 100°C or more lower than the glass transition temperature of the hydrophilic resin contained in the hydrophilic resin layer. From the viewpoint of water repellency, anti-reflection properties, etc., the glass transition temperature of the hydrophobic resin is preferably -150°C to 70°C, more preferably -100°C to 20°C, and even more preferably -100°C to 0°C. In the present disclosure, the glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), and more specifically, is determined from the "extrapolated glass transition onset temperature" described in JIS K 7121 (1987) "Method for determining the glass transition temperature of plastics."

[0016] From the viewpoint of water repellency, anti-reflection properties, etc., the mass melt flow rate (MFR) of the hydrophobic resin is preferably 0.1 g / 10 min to 100 g / 10 min, more preferably 0.3 g / 10 min to 30 g / 10 min, and even more preferably 2 g / 10 min to 20 g / 10 min. In the present disclosure, the mass melt flow rate is determined using an extrusion blastometer (capillary rheometer), and more specifically, is determined by the method described in JIS K7210-1 "Method for determining melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastics - thermoplastics."

[0017] From the viewpoint of water repellency, anti-reflection properties, etc., the content of the hydrophobic resin relative to the total mass of the hydrophobic resin layer is preferably 70 mass% or more, more preferably 80 mass% or more, even more preferably 90 mass% or more, and may be 100 mass%.

[0018] The hydrophobic resin layer may contain additives such as surfactants, pigments, dyes, ultraviolet absorbers, light stabilizers, antioxidants, rust inhibitors, adhesion promoters, thermal polymerization inhibitors, and inorganic particles.

[0019] From the viewpoint of water repellency, anti-reflection properties, etc., the thickness of the hydrophobic resin is preferably 1 μm to 20 μm, more preferably 3 μm to 15 μm, and even more preferably 5 μm to 10 μm.

[0020] The method for forming the hydrophobic resin layer on the surface of the support is not particularly limited, and examples thereof include a method in which a hydrophobic resin composition containing the above-mentioned hydrophobic resin, etc. is applied to the surface of the support and dried. The hydrophobic resin composition may contain an organic solvent.

[0021] The support may contain one or more resins, and examples of the resin include polyester resin, polyolefin resin, (meth)acrylic resin, polyamide resin, polyimide resin, polyamideimide resin, etc. Among the above, from the viewpoints of transparency and mechanical strength, the support preferably contains a polyester resin, and more preferably contains polyethylene terephthalate.

[0022] The content of the resin relative to the total mass of the support is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass.

[0023] The support may contain the above-mentioned additives.

[0024] From the viewpoint of reflection suppression, the total light transmittance of the support is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more. In the present disclosure, the total light transmittance is measured in accordance with the method specified in JIS K 7375 (2008).

[0025] The support is preferably a film containing the above-mentioned resin, and from the viewpoints of mechanical strength and solvent resistance, is more preferably a biaxially stretched film.

[0026] From the viewpoint of the retention of the hydrophobic resin layer and the like, the thickness of the support is preferably 1 μm to 50 μm, more preferably 10 μm to 40 μm, and even more preferably 15 μm to 30 μm.

[0027] (Step of forming hydrophilic resin layer) The method for producing a laminate of the present disclosure includes a step of forming a hydrophilic resin layer containing a hydrophilic resin on the surface of a hydrophobic resin layer. The hydrophilic resin layer may contain two or more types of hydrophilic resin. The hydrophilic resin is preferably soluble in water (25°C, pH 7) or methanol (25°C) at a concentration of 0.1 mass% or more.

[0028] Examples of hydrophilic resins include (meth)acrylic resins, styrene (meth)acrylic resins, epoxy resins, polyurethane resins, nylon resins, butyral resins, vinyl alcohol resins, polyvinylpyrrolidone resins, and cellulose resins. Among these, (meth)acrylic resins are preferred from the viewpoint of water repellency. Furthermore, (meth)acrylic resins are also preferred from the viewpoint of reducing the static friction coefficient against glass. When the laminate produced by the production method of the present disclosure includes a photosensitive resin layer, reducing the static friction coefficient of the hydrophilic resin layer against glass can improve the slipperiness (hereinafter also simply referred to as slipperiness) of the film on the hydrophilic resin layer side obtained by peeling the interface between the hydrophobic resin layer and the hydrophilic resin layer against a photomask (substrate material: glass), thereby enabling good exposure of the photosensitive resin layer.

[0029] The hydrophilic resin contains a structural unit having a polar group. From the viewpoint of water repellency, slipperiness, etc., the content of the structural unit having a polar group relative to the total amount of all structural units contained in the hydrophilic resin is preferably 10% by mass to 40% by mass, more preferably 13% by mass to 37% by mass, and even more preferably 15% by mass to 35% by mass.

[0030] From the viewpoint of water repellency, slipperiness, etc., the structural unit having a polar group is preferably a structural unit corresponding to (meth)acrylic acid.

[0031] From the viewpoint of water repellency, slipperiness, etc., the acid value of the hydrophilic resin is preferably 150 mgKOH / g or more, and more preferably 150 mgKOH / g to 300 mgKOH / g. In the present disclosure, the acid value is measured according to the method described in JIS K0070 (1992).

[0032] From the viewpoint of water repellency, slipperiness, etc., the glass transition temperature of the hydrophilic resin is preferably 30°C or higher, more preferably 50 to 180°C, and even more preferably 90 to 150°C.

[0033] From the viewpoint of water repellency, slipperiness, etc., the weight-average molecular weight of the hydrophilic resin is preferably 5,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 80,000. In the disclosure, unless otherwise specified, the weight-average molecular weight is a molecular weight detected with a gel permeation chromatography (GPC) analyzer using a column of TSKgel Super HM-H (trade name of Tosoh Corporation) in a solvent of PFP (pentafluorophenol) / chloroform = 1 / 2 (mass ratio) and a differential refractometer, and converted using polystyrene as a standard substance.

[0034] From the viewpoint of water repellency, slipperiness, etc., the content of the hydrophilic resin relative to the total mass of the hydrophilic resin layer is preferably 70 mass% or more, more preferably 80 mass% or more, even more preferably 90 mass% or more, and may be 100 mass%.

[0035] The hydrophilic resin layer may contain the above-mentioned additives.

[0036] From the viewpoint of water repellency, slipperiness, etc., the thickness of the hydrophilic resin is preferably 0.1 μm or more, more preferably 0.5 μm to 10 μm, and even more preferably 1 μm to 5 μm.

[0037] The method for forming the hydrophilic resin layer on the surface of the hydrophobic resin layer is not particularly limited, and examples thereof include a method in which a hydrophilic resin composition containing the above-mentioned hydrophilic resin, etc. is applied to the surface of a support and then dried. The hydrophilic resin composition may contain an organic solvent.

[0038] (Step of forming convex structure and concave structure) The method for producing a laminate according to the present disclosure includes the steps of applying a specific composition to the surface of a hydrophilic resin layer, drying the composition, and forming a convex structure on the hydrophilic resin layer-side surface of the hydrophobic resin layer and a concave structure on the hydrophobic resin layer-side surface of the hydrophilic resin layer.

[0039] The mechanism by which a convex structure is formed on the hydrophilic resin layer-side surface of the hydrophobic resin layer and a concave structure is formed on the hydrophobic resin layer-side surface of the hydrophilic resin layer is not clear, but is presumed to be as follows: The specific composition applied to the surface of the hydrophilic resin layer permeates from the hydrophilic resin layer toward the hydrophobic resin layer. The specific composition is then heated and dried, causing foaming of the specific composition. The foaming of the specific composition occurs by expanding as bubbles from the hydrophobic resin layer, which is less plasticized by the specific composition, toward the interior of the hydrophilic resin layer, which is more plasticized by the specific composition and is sufficiently softened. In this way, a concave structure is formed on the hydrophobic resin layer-side surface of the hydrophilic resin layer. The gaseous specific composition is then gradually absorbed into the hydrophilic resin layer, and the area where the foamed gas was present becomes a vacuum space. As the specific composition evaporates out of the system, the hydrophobic resin layer is drawn toward the space in the hydrophilic resin layer, which is sufficiently harder than the hydrophobic resin layer, resulting in the formation of a convex structure on the hydrophilic resin layer-side surface of the hydrophobic resin layer. Furthermore, when the hydrophilic resin layer and the hydrophobic resin layer are separated by peeling, the protrusions of the hydrophobic resin layer that have penetrated into the hydrophilic resin layer may be elongated and may be deformed into protrusions with a high aspect ratio. It is presumed that the above-mentioned convex structure imparts excellent functionality such as water repellency and anti-reflection properties to the surface of the hydrophobic resin layer, and the above-mentioned concave structure imparts excellent functionality such as water repellency and slipperiness to the surface of the hydrophilic resin layer. The water repellency can be explained as the lotus leaf effect (lotus effect), and the anti-reflection properties can be explained as the moth-eye effect.

[0040] The specific composition contains an alcohol. The specific composition may contain two or more types of alcohol. Examples of the alcohol include methanol, ethanol, propanol, and butanol. Methanol is preferred from the viewpoints of water repellency, anti-reflection properties, slip properties, and the like.

[0041] From the viewpoints of water repellency, anti-reflection properties, slip properties, and the like, the content of alcohol relative to the total mass of the specific composition is preferably 30% by mass to 70% by mass, more preferably 40% by mass to 65% by mass, and even more preferably 45% by mass to 60% by mass.

[0042] From the viewpoint of water repellency, anti-reflection properties, slip properties, etc., the specific composition preferably contains water.

[0043] When the specific composition contains water, from the viewpoints of water repellency, anti-reflection properties, slip properties, etc., the ratio of the water content to the alcohol content (water content / alcohol content) is preferably 1 / 9 to 5 / 5, more preferably 2 / 8 to 4 / 6, and even more preferably 2 / 8 to 3 / 7.

[0044] The specific composition may contain a water-soluble resin. By including a water-soluble resin in the specific composition, the above-mentioned convex and concave structures can be formed, and a water-soluble intermediate layer can be formed on the surface of the hydrophilic resin layer. The specific composition may contain two or more water-soluble resins. In the present disclosure, a water-soluble resin refers to a resin that dissolves at least 1 g in 100 g of water at pH 7.0 at 23°C. The water-soluble resin preferably has the above-mentioned polar group. Examples of water-soluble resins include polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), water-soluble polysaccharides (e.g., methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, propyl methyl cellulose), pullulan, starch (e.g., hydroxypropyl starch, carboxymethyl starch), chitosan, cyclodextrin, polyethylene oxide, polyethyloxazoline, methylol melamine, polyacrylamide, and phenolic resins.

[0045] From the viewpoints of water repellency, anti-reflection properties, slip properties, and the like, the content of the water-soluble resin relative to the total mass of the specific composition is preferably 1% by mass to 15% by mass, more preferably 2% by mass to 13% by mass, and even more preferably 3% by mass to 10% by mass.

[0046] The specific composition may contain a water-insoluble resin. By including a water-insoluble resin in the specific composition, the above-mentioned convex and concave structures can be formed, and a water-soluble intermediate layer can be formed on the surface of the hydrophilic resin layer. The specific composition may contain two or more water-soluble resins. In the present disclosure, the water-insoluble resin refers to a resin that dissolves in an amount of less than 1 g per 100 g of water at pH 7.0 at 23°C. Examples of water-insoluble resins include styrene particle water dispersions, methyl methacrylate water dispersions, acrylic resin water dispersions, polyolefin resin water dispersions, polyester resin water dispersions, polyurethane resin water dispersions, and epoxy resin water dispersions.

[0047] From the viewpoints of water repellency, anti-reflection properties, slip properties, and the like, the content of the water-insoluble resin relative to the total mass of the specific composition is preferably 1% by mass to 15% by mass, more preferably 2% by mass to 13% by mass, and even more preferably 3% by mass to 10% by mass.

[0048] The specific composition may contain the above-mentioned additives. The specific composition may also contain an organic solvent other than alcohol.

[0049] From the viewpoint of water repellency, anti-reflection, slipperiness, etc., the coating amount of the specific composition is 10 mL / m ２ ~45mL / m ２ Preferably, the concentration is 15 mL / m ２ ~40 mL / m ２ More preferably, it is 20 mL / m ２ ~30 mL / m ２ When the water-soluble intermediate layer is formed from the specific composition, the thickness of the water-soluble intermediate layer is preferably 0.01 μm to 10 μm, and more preferably 0.1 μm to 2 μm, from the viewpoints of water repellency, anti-reflection properties, slip properties, etc.

[0050] From the viewpoints of water repellency, anti-reflection properties, slip properties, etc., the drying temperature of the specific composition is preferably 50° C. to 100° C., and more preferably 60° C. to 90° C. In the present disclosure, the drying temperature refers to the temperature of the environment in which the specific composition is dried, and does not refer to the temperature of the specific composition.

[0051] (Step of forming photosensitive resin layer) The method for producing a laminate according to the present disclosure may include a step of forming a photosensitive resin layer on the surface of a hydrophilic resin layer after applying and drying a specific composition, or, as will be described later, when a water-soluble intermediate layer is formed using a specific composition, a method for producing a laminate according to the present disclosure may include a step of forming a photosensitive resin layer on the surface of a hydrophilic resin layer.

[0052] The photosensitive resin layer may be a negative photosensitive resin layer or a positive photosensitive resin layer.

[0053] The photosensitive resin layer may contain one or more polymers having an acid group (hereinafter simply referred to as polymers). Examples of the acid group include a carboxy group, a sulfo group, a phosphate group, and a phosphonate group. The acid group is preferably a carboxy group.

[0054] From the viewpoint of alkali developability, the polymer is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and more preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more. The polymer may have a reactive group. The reactive group is preferably a polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated group, a polycondensable group (e.g., a hydroxy group, a carboxy group), and a polyaddition reactive group (e.g., an epoxy group, an isocyanate group).

[0055] From the viewpoint of alkali developability, the acid value of the polymer is preferably from 60 mgKOH / g to 200 mgKOH / g, more preferably from 100 mgKOH / g to 200 mgKOH / g, and particularly preferably from 150 mgKOH / g to 200 mgKOH / g.

[0056] The weight average molecular weight of the polymer is preferably 1,000 or more, more preferably 10,000 or more, and particularly preferably 20,000 to 100,000.

[0057] The polymer may have a structural unit derived from a non-acidic monomer, such as a (meth)acrylic acid ester, a vinyl alcohol ester compound, (meth)acrylonitrile, or an aromatic vinyl compound.

[0058] Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and benzyl (meth)acrylate. Examples of vinyl alcohol ester compounds include vinyl acetate. Examples of aromatic vinyl compounds include styrene and styrene derivatives. The non-acidic monomer is preferably one or more monomers selected from the group consisting of methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, styrene derivatives, and benzyl (meth)acrylate.

[0059] From the viewpoint of photosensitivity, the content of the polymer is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and even more preferably 30% by mass to 70% by mass, relative to the total mass of the photosensitive resin layer.

[0060] The photosensitive resin layer may contain one or more polymerizable compounds. The polymerizable compound is not limited, and known polymerizable compounds can be used. The polymerizable compound is preferably an ethylenically unsaturated compound. The ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups. The ethylenically unsaturated group is preferably a (meth)acryloyl group. The ethylenically unsaturated compound is preferably a (meth)acrylate compound. As the ethylenically unsaturated compound, an ethylenically unsaturated compound having a bisphenol structure is also preferably used. As the ethylenically unsaturated compound having a bisphenol structure, alkylene oxide-modified bisphenol A di(meth)acrylate can be used. Examples of alkylene oxide-modified bisphenol A di(meth)acrylates include ethylene glycol dimethacrylates in which an average of 5 moles of ethylene oxide have been added to each end of bisphenol A, ethylene glycol dimethacrylates in which an average of 2 moles of ethylene oxide have been added to each end of bisphenol A, ethylene glycol dimethacrylates in which an average of 5 moles of ethylene oxide have been added to each end of bisphenol A, alkylene glycol dimethacrylates in which an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide have been added to each end of bisphenol A, and alkylene glycol dimethacrylates in which an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide have been added to each end of bisphenol A. Specific examples of alkylene oxide-modified bisphenol A di(meth)acrylates include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane and 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane.

[0061] The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200. When the polymerizable compound is a compound having a molecular weight distribution (for example, a polymer), the weight average molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

[0062] The content of the polymerizable compound is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass, relative to the total mass of the photosensitive resin layer.

[0063] The photosensitive resin layer may contain a polymerization initiator, and any conventionally known photoradical polymerization initiator may be used as the polymerization initiator.

[0064] The content of the polymerization initiator relative to the total mass of the photosensitive resin layer is not particularly limited, and can be set to 0.01% by mass to 1% by mass.

[0065] The photosensitive resin layer may contain the above-mentioned additives.

[0066] The thickness of the photosensitive resin layer is not particularly limited, and can be set to 0.5 μm to 5 μm.

[0067] The method for forming the photosensitive resin layer is not particularly limited, and examples include a method in which a photosensitive resin layer-forming composition containing the above-mentioned photosensitive resin or the like is applied to the surface of the hydrophilic resin layer or the surface of the water-soluble intermediate layer and dried. The photosensitive resin layer-forming composition may contain an organic solvent. From the viewpoints of water repellency, reflection suppression, slipperiness, etc., the alcohol content relative to the total mass of the photosensitive resin layer-forming composition is preferably 50% by mass or less, more preferably 10% by mass or less. From the viewpoints of water repellency, reflection suppression, slipperiness, etc., the water content relative to the total mass of the photosensitive resin layer-forming composition is preferably 5% by mass or less, more preferably 1% by mass or less, and particularly preferably zero.

[0068] [Film Manufacturing Method] The film manufacturing method of the present disclosure includes the steps of manufacturing a laminate using the laminate manufacturing method described above (hereinafter referred to as the laminate manufacturing step), and peeling the hydrophobic resin layer and hydrophilic resin layer of the laminate at their interface (hereinafter referred to as the peeling step). According to the film manufacturing method described above, it is possible to manufacture a film (hereinafter referred to as specific film A) that is made of a hydrophobic resin layer on the surface of a support and has a convex structure on its surface, and a film (hereinafter referred to as specific film B) that is made of a hydrophilic resin layer and has a concave structure on its surface. The laminate manufacturing step will not be described here.

[0069] [Peeling Step] The film manufacturing method of the present disclosure includes a step of peeling the hydrophobic resin layer and the hydrophilic resin layer of the laminate at their interface. The peeling method is not particularly limited, and may be performed manually or using a peeling device.

[0070] From the viewpoint of peeling without destroying the convex structure formed on specific film A and the concave structure formed on specific film B, the peel strength of the hydrophobic resin layer and the hydrophilic resin layer is preferably 0.5 g / cm to 50 g / cm, and more preferably 0.5 g / cm to 10 g / cm. In the present disclosure, the peel strength is measured by a testing machine in an environment of 25°C, at a rate of 300 mm / min, when the hydrophobic resin layer is peeled from the hydrophilic resin layer in a 180° direction.

[0071] From the viewpoints of water repellency, anti-reflection properties, etc., the major axis of the convex structures on the surface of specific film A is preferably 0.02 μm to 5 μm, more preferably 0.02 μm to 1 μm, and even more preferably 0.02 μm to 0.4 μm. In the present disclosure, the major axis of the convex structures is determined as follows. First, an SEM image of the surface of the film on which the convex structures are formed is obtained using a scanning electron microscope (SEM). On the convex structures in the SEM image, the distance between the two points with the longest distance is measured, and this is taken as the major axis of the convex structures.

[0072] From the viewpoint of water repellency, anti-reflection properties, etc., the average height of the convex structures on the surface of Specific Film A is preferably 10 nm to 3000 nm, more preferably 30 nm to 1000 nm, and even more preferably 100 nm to 500 nm. In the present disclosure, the average height of the convex structures is measured as follows. First, a film test piece is prepared using an ultramicrotome, and an SEM image of the cross section is obtained using a scanning electron microscope. Three convex structures are arbitrarily selected from the SEM image, and the maximum height difference is measured as the height, and the average is calculated to be the average height of the convex structures.

[0073] From the viewpoint of water repellency, anti-reflection properties, etc., the surface of the specific film A has a convex structure of 10 μm on the surface. ２ Preferably, 1 to 1000 convex structures are formed per film, more preferably 10 to 900, and even more preferably 30 to 850. In the present disclosure, the number of convex structures is measured from an SEM image of the surface of the film on which the convex structures are formed.

[0074] From the viewpoint of water repellency, the water contact angle of the surface of Specific Film A on which the convex structure is formed is preferably 100° or more, more preferably 105° or more, and even more preferably 110° or more at 25°C. In the present disclosure, the water contact angle is measured in accordance with the sessile drop method of JIS R 3257 (1999).

[0075] From the viewpoint of anti-reflection properties, the reflectance when the surface of the specific film A having the convex structure formed thereon is irradiated with light having a wavelength of 550 nm is preferably 4% or less, and more preferably 3% or less, where the incident angle of the light is 0°.

[0076] From the viewpoints of water repellency, slipperiness, etc., the major axis of the recessed structure in Specific Film B is preferably 0.02 μm to 5 μm, more preferably 0.02 μm to 1 μm, and even more preferably 0.02 μm to 0.4 μm. In the present disclosure, the major axis of the recessed structure is determined as follows. First, an SEM image of the surface of the film on which the recessed structure is formed is obtained using a scanning electron microscope (SEM). On the recessed structure in the SEM image, the distance between the two points with the longest distance is measured, and this is taken as the major axis of the convex structure.

[0077] From the viewpoints of water repellency, slipperiness, etc., the average depth of the recessed structures in Specific Film B is preferably 10 nm to 3000 nm, more preferably 30 nm to 1000 nm, and even more preferably 100 nm to 500 nm. In the present disclosure, the average depth of the recessed structures is determined as follows. First, a test piece of the film is prepared using an ultramicrotome, and an SEM image of the cross section is obtained using a scanning electron microscope. Three recessed structures are arbitrarily selected from the SEM image, and the maximum height difference is measured as the depth. The average of these values ​​is calculated and used as the average depth of the recessed structures.

[0078] From the viewpoint of water repellency, slipperiness, etc., the surface of specific film B has a recessed structure of 10 μm on the surface. ２ Preferably, 1 to 1000 recessed structures are formed per film, more preferably 10 to 900, and even more preferably 30 to 850. In the present disclosure, the number of recessed structures is measured from an SEM image of the surface of the film on which the recessed structures are formed.

[0079] At 25°C, the water contact angle of the surface of specific film B on which the recessed structure is formed is preferably 95° or more, more preferably 105° or more, and even more preferably 110° or more, from the viewpoint of water repellency.

[0080] From the viewpoint of slipperiness, the static friction coefficient of the surface of specific film B on which the recessed structure is formed against glass is preferably 1.50 or less, more preferably 1.00 or less, and even more preferably 0.85 or less. The lower limit of the static friction coefficient is not particularly limited and can be 0.1 or more. In the present disclosure, the static friction coefficient is measured in an environment of 25°C and relative humidity 50% in accordance with JIS K 7125 (1999).

[0081] [Film with Convex Structure] The film of the present disclosure contains a hydrophobic resin, and has convex structures on at least one surface, the convex structures having a major axis of 0.02 μm to 5 μm and an average height of 10 nm to 3000 nm, and ２ 1 to 1000 pieces are formed per unit area.

[0082] The hydrophobic resin has been described above, so a description thereof will be omitted here.

[0083] From the viewpoint of water repellency, anti-reflection properties, etc., the content of the hydrophobic resin relative to the total mass of the film is preferably 70 mass% or more, more preferably 80 mass% or more, even more preferably 90 mass% or more, and may be 100 mass%.

[0084] The film may contain a surfactant and the above-mentioned additives.

[0085] From the viewpoint of water repellency, anti-reflection properties, etc., the major axis of the convex structure is preferably 0.02 μm to 5 μm, more preferably 0.02 μm to 1 μm, and even more preferably 0.02 μm to 0.4 μm. The major axis of the convex structure is measured by the same method as described above.

[0086] From the viewpoint of water repellency, anti-reflection properties, etc., the average height of the convex structures is preferably 30 nm to 1000 nm, and more preferably 100 nm to 500 nm. The average height of the convex structures is measured by the same method as described above.

[0087] From the viewpoint of water repellency and anti-reflection properties, the convex structure is 10 μm thick on the surface. ２Preferably, 10 to 900 particles are formed per unit area, and more preferably, 30 to 850 particles are formed per unit area.

[0088] From the viewpoint of water repellency, the water contact angle of the film surface on which the convex structures are formed at 25° C. is preferably 100° or more, more preferably 105° or more, and even more preferably 110° or more. The number of convex structures is measured by the same method as described above.

[0089] From the viewpoint of anti-reflection properties, the reflectance when the surface of the film having the convex structure formed thereon is irradiated with light having a wavelength of 550 nm is preferably 4% or less, and more preferably 3% or less, where the incident angle of the light is 0°.

[0090] From the viewpoint of water repellency, anti-reflection properties, etc., the thickness of the film is preferably 1 μm to 20 μm, more preferably 3 μm to 15 μm, and even more preferably 5 μm to 10 μm.

[0091] Applications of the film of the present disclosure include water-repellent films, antifouling films, highly transparent films, and antireflection films.

[0092] The film of the present disclosure can be produced by the film production method described above.

[0093] [Supported Film] The supported film of the present disclosure comprises a support and the film having the above-described convex structure provided on one surface of the support, and the surface of the film having the convex structure opposite to the surface on which the convex structure is formed is in contact with the support. The film having the convex structure and the support have been described above, so further description will be omitted here.

[0094] From the viewpoint of film transparency, the supported film of the present disclosure preferably has a film having a convex structure on both sides of the support and a light transmittance of 92% or more at a wavelength of 550 nm. If the convex structure is on only one side, only half of the transparency improvement effect of the film due to antireflection is obtained, and the transmittance improvement effect is halved due to reflection from the non-antireflection side without the convex structure, so it is preferable that a film having a convex structure is provided on both sides of the support. The light transmittance is more preferably 94% or more. The incident angle of light is 0°.

[0095] The supported film of the present disclosure can be used in applications such as a water-repellent film, an antifouling film, a highly transparent film, and an antireflection film.

[0096] [Film with Concave Structure] The film of the present disclosure contains a hydrophilic resin, and has a concave structure on at least one surface, the concave structure having a major axis of 0.02 μm to 5 μm and an average depth of 10 nm to 3000 nm, and ２ 1 to 1000 pieces are formed per unit area.

[0097] The hydrophilic resin has been described above, so a description thereof will be omitted here.

[0098] From the viewpoint of water repellency, slipperiness, etc., the content of the hydrophilic resin relative to the total mass of the film is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass.

[0099] The film may contain the additives described above.

[0100] From the viewpoint of water repellency, slipperiness, etc., the major axis of the recessed structure is preferably 0.02 μm to 5 μm, more preferably 0.02 μm to 1 μm, and even more preferably 0.02 μm to 0.4 μm. The major axis of the recessed structure is measured by the same method as described above.

[0101] From the viewpoint of water repellency, slipperiness, etc., the average depth of the recessed structure is preferably 30 nm to 1000 nm, and more preferably 100 nm to 500 nm. The average depth of the recessed structure is measured by the same method as described above.

[0102] From the viewpoint of water repellency and slipperiness, the concave structure is 10 μm on the surface. ２ Preferably, 10 to 900 recessed structures are formed per unit area, and more preferably, 30 to 850 recessed structures are formed per unit area. The number of recessed structures is measured by the same method as described above.

[0103] From the viewpoint of water repellency, the water contact angle of the surface of the film having the recessed structure formed thereon at 25° C. is preferably 95° or more, more preferably 105° or more, and even more preferably 110° or more. The water contact angle is measured by the same method as described above.

[0104] From the viewpoint of slipperiness, the static friction coefficient of the surface of the film of the present disclosure on which the recessed structure is formed against glass is preferably 1.50 or less, more preferably 1.00 or less, and even more preferably 0.85 or less. The lower limit of the static friction coefficient is not particularly limited and can be 0.1 or more. The static friction coefficient is measured by the same method as described above.

[0105] Applications of the film of the present disclosure include water-repellent films, antifouling films, easy-slip films, and surface films for photosensitive transfer materials.

[0106] The film of the present disclosure can be produced by the film production method described above.

[0107] [Photosensitive Transfer Material] The photosensitive transfer material of the present disclosure comprises a support, a hydrophobic resin layer, a hydrophilic resin layer, a water-soluble intermediate layer, and a photosensitive resin layer in this order, wherein the hydrophobic resin layer contains a polyolefin resin, the hydrophilic resin layer contains a (meth)acrylic resin, and the water-soluble intermediate layer contains a water-soluble resin, and the hydrophobic resin layer and the hydrophilic resin layer are peelable at their interface, and the hydrophilic resin layer has a 10 μm thick film on the surface of the hydrophobic resin layer side. ２The depressions have a major axis of 0.02 μm to 5 μm and an average depth of 10 nm to 3000 nm, and the coefficient of static friction of the surface against glass is 1.50 or less.

[0108] The support, hydrophobic resin layer, hydrophilic resin layer, water-soluble intermediate layer, and photosensitive resin layer provided in the photosensitive transfer material of the present disclosure are as described above, and therefore will not be described here. Furthermore, the preferred ranges of the number, major axis, and average depth of the recessed structures of the hydrophilic resin layer are as described above, and therefore will not be described here. Furthermore, the preferred ranges of the static friction coefficient of the surface of the hydrophilic resin layer on which the recessed structures are formed against glass are as described above, and therefore will not be described here.

[0109] The hydrophobic resin layer may have a convex structure formed on the surface facing the hydrophilic resin layer. The preferred ranges for the number, major axis, and average depth of the convex structures are as described above, and therefore will not be described here. The preferred ranges for the water contact angle of the surface of the hydrophobic resin layer on which the convex structures are formed and the reflectance when irradiated with light having a wavelength of 550 nm are as described above, and therefore will not be described here.

[0110] The photosensitive transfer material of the present disclosure is peelable at the interface between the hydrophobic resin layer and the hydrophilic resin layer. This allows a transfer layer having a hydrophilic resin layer, a water-soluble intermediate layer, and a photosensitive resin layer in this order to be transferred to the surface of a transfer recipient. The preferred numerical ranges for the peel strength of the hydrophobic resin layer and the hydrophilic resin layer are also as described above, and will not be described here.

[0111] The film of the present disclosure can be produced by the above-described method for producing a laminate.

[0112] The above embodiment will be specifically described below using examples, but the above embodiment is not limited to these examples.

[0113] Example 1-1: A 25 μm thick polyethylene terephthalate (PET) film (total light transmittance 91%, biaxially stretched film) was prepared as a support. A hydrophobic resin composition having the following composition was melt-extruded onto one surface of the support to form a 5 μm thick hydrophobic resin layer.

[0114] - Hydrophobic resin composition - 100 parts by mass of polyethylene A (LLDPE, Tg -70°C or less, MFR 8g / 10min to 10g / 10min, manufactured by Prime Polymer Co., Ltd., Evolue (registered trademark) SP1071C)

[0115] A hydrophilic resin composition having the following composition was applied to the surface of the hydrophobic resin layer and then dried in an oven at 80°C for 1 minute to form a hydrophilic resin layer having a thickness of 2.4 μm. (Meth)acrylic resin A was a 1:1 mixed solution (solid concentration: 30.0% by mass) of a copolymer of styrene, methacrylic acid, and methyl methacrylate (monomer content: 52% by mass / 29% by mass / 19% by mass, Mw: 70,000, Tg: 130°C, acid value: 189 mg KOH / g) with propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether.

[0116] - Hydrophilic Resin Composition A-1 - (Meth)acrylic resin A-1 59.4 parts by mass Surfactant (MEGAFACE (registered trademark) F552, manufactured by DIC Corporation) 0.03 parts by mass Propylene glycol monomethyl ether acetate 10.6 parts by mass Methyl ethyl ketone 94.2 parts by mass Propylene glycol monomethyl ether 15.7 parts by mass

[0117] The specific composition shown below was applied to the surface of the hydrophilic resin layer and dried in an oven at 80°C for 1 minute to form a water-soluble intermediate layer having a thickness of 1.0 µm, thereby obtaining a specific laminate. ２-Specific composition- Methanol 57.0 parts by mass Water 38.0 parts by mass Polyvinyl alcohol A (PVA, manufactured by Mitsubishi Chemical Corporation, Gohsenex (registered trademark) CSK-50) 1.67 parts by mass Polyvinyl alcohol B (PVA, manufactured by Nippon Vinyl Acetate & Poval Co., Ltd., JMR-3H) 1.67 parts by mass Polyvinylpyrrolidone (PVP, manufactured by Ashland Co., Ltd., PVP-K30) 1.67 parts by mass Surfactant (manufactured by DIC Corporation, Megafac (registered trademark) F444) 0.005 parts by mass

[0118] After the specific composition was applied and dried, a composition for forming a photosensitive resin layer having the following composition was applied to the surface of the water-soluble intermediate layer and dried in an oven at 80°C for 1 minute to form a photosensitive resin layer having a thickness of 2.2 μm. -Composition B-1 for forming photosensitive resin layer- 0.92 parts by mass of polymerizable compound (Aronix (registered trademark) M270, manufactured by Toagosei Co., Ltd.) 8.78 parts by mass of polymerizable compound (2,2-bis[4-(methacryloxypentaethoxy)phenyl]propane, manufactured by Shin-Nakamura Chemical Co., Ltd., BPE500) 39.43 parts by mass of polymer having acid group: (meth)acrylic resin A 0.070 parts by mass of photoradical polymerization initiator (4,4'-bis(diethylamino)benzophenone, manufactured by Tokyo Chemical Industry Co., Ltd., EAB-F) 1.61 parts by mass of photopolymerization initiator ("B-CIM": 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer (manufactured by Hampford Research)) Chain transfer agent (N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)) 0.032 parts by mass Polymerization inhibitor ("1-phenyl-3-pyrazolidone": manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., MEK solution with a concentration of 1% by mass) 0.24 parts by mass Polymerization inhibitor ("phenothiazine": manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) 0.063 parts by mass Rust inhibitor (carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd., CBT-1) 0.023 parts by mass Surfactant (manufactured by DIC Corporation, F-552) 0.25 parts by mass Methyl ethyl ketone 82.5 parts by mass 1-methoxy-2-propyl acetate 37.9 parts by mass Methanol 4.7 parts by mass Propylene glycol monomethyl ether (manufactured by Wako Pure Chemical Industries, Ltd., MFG) 3.5 parts by mass

[0119] The photosensitive resin layer of the specific laminate was laminated onto the copper foil side surface of a copper foil-attached polyethylene terephthalate film (hereinafter referred to as the copper-attached PET film). The lamination conditions were a roll temperature of 100°C and a lamination speed of 4 m / min. After lamination onto the copper-attached PET film, the hydrophilic and hydrophobic resin layers of the specific laminate were peeled off at the interface, yielding a specific film A (hydrophobic resin layer) having a convex structure formed on the surface of the support, and a specific film B (hydrophilic resin layer) having a concave structure formed on the surface of the copper-attached PET film.

[0120] An SEM image of the surface of specific film A on which the convex structures were formed was obtained using a scanning electron microscope (Hitachi High-Tech S-4800, magnification 30,000 times). The SEM image is shown in Figure 1. When the major axis of the convex structures was measured from the SEM image, it was in the range of 0.18 μm to 0.53 μm, and the major axis of the convex structures was in the range of 10 μm on the surface. ２ It was confirmed that 122 convex structures were formed per 1000 μm. A test piece of specific film A was prepared using an ultramicrotome, and an SEM image of the cross section was obtained using the scanning electron microscope. The average height of the convex structures was measured and found to be 62 nm.

[0121] The major axis of the recessed structure on the surface of specific film B was measured in the same manner as for the protruding structure, and was found to be in the range of 0.12 μm to 0.74 μm. ２ It was confirmed that 72 recessed structures were formed per film. An SEM image is shown in Figure 2. An SEM image of the cross section of specific film B was obtained in the same manner as for specific film A, and the average depth of the recessed structures was measured, which was 72 nm.

[0122] Example 1-2 A specific laminate, specific film A, and specific film B were produced in the same manner as in Example 1-1, except that the thickness of the hydrophilic resin layer was changed to 1.6 μm.

[0123] In the same manner as in Example 1-1, the major axis of the convex structure of specific film A was measured and found to be in the range of 0.08 μm to 0.18 μm. ２It was confirmed that 837 convex structures were formed per one sample. The average height of the convex structures was measured in the same manner as in Example 1-1 and was found to be 31 nm.

[0124] In the same manner as in Example 1-1, the major axis of the recessed structure of specific film B was measured and found to be in the range of 0.04 μm to 0.14 μm. ２ It was confirmed that 826 recessed structures were formed per square meter. The average depth of the recessed structures was measured in the same manner as in Example 1-1 and was found to be 45 nm.

[0125] Example 1-3 A specific laminate, a specific film A, and a specific film B were produced in the same manner as in Example 1-2, except that the ratio of the water content to the methanol content in the specific composition (water content / methanol content) was changed to 3 / 7.

[0126] In the same manner as in Example 1-1, the major axis of the convex structure of specific film A was measured and found to be in the range of 0.13 μm to 0.26 μm. ２ It was confirmed that 566 convex structures were formed per square meter. The average height of the convex structures was measured in the same manner as in Example 1-1 and was found to be 54 nm.

[0127] In the same manner as in Example 1-1, the major axis of the recessed structure of specific film B was measured and found to be in the range of 0.06 μm to 0.19 μm. ２ It was confirmed that 525 recessed structures were formed per square meter. The average depth of the recessed structures was measured in the same manner as in Example 1-1 and was found to be 56 nm.

[0128] Example 1-4 A specific laminate, a specific film A, and a specific film B were produced in the same manner as in Example 1-2, except that the ratio of the water content to the methanol content in the specific composition (water content / methanol content) was changed to 2 / 8.

[0129] In the same manner as in Example 1-1, the major axis of the convex structure of specific film A was measured and found to be in the range of 0.08 μm to 0.24 μm. ２It was confirmed that 269 convex structures were formed per square meter. An SEM image is shown in Figure 3. The average height of the convex structures was measured in the same manner as in Example 1-1 and was found to be 355 nm.

[0130] In the same manner as in Example 1-1, the major axis of the recessed structure of specific film B was measured and found to be in the range of 0.08 μm to 0.29 μm. ２ It was confirmed that 400 recessed structures were formed per square meter. An SEM image is shown in Figure 4. The average depth of the recessed structures was measured in the same manner as in Example 1-1 and was found to be 126 nm.

[0131] Example 1-5 A specific laminate, a specific film A, and a specific film B were produced in the same manner as in Example 1-2, except that the hydrophobic resin composition was changed to the following composition and the thickness of the hydrophobic resin layer was changed to 10 μm.

[0132] - Hydrophobic resin composition - Polyethylene B (LDPE, Tg -70°C or less, MFR 8g / 10min to 10g / 10min, manufactured by Tosoh Corporation, Petrothene DLZ19A) 100 parts by mass

[0133] In the same manner as in Example 1-1, the major axis of the convex structure of specific film A was measured and found to be in the range of 0.16 μm to 0.82 μm. ２ It was confirmed that 115 convex structures were formed per square meter. The average height of the convex structures was measured in the same manner as in Example 1-1 and was found to be 65 nm.

[0134] In the same manner as in Example 1-1, the major axis of the recessed structure of specific film B was measured and found to be in the range of 0.21 μm to 0.80 μm. ２ It was confirmed that 49 recessed structures were formed per square meter. The average depth of the recessed structures was measured in the same manner as in Example 1-1 and was found to be 163 nm.

[0135] Example 1-6 A specific laminate, specific film A, and specific film B were produced in the same manner as in Example 1-2, except that the hydrophobic resin composition was changed to the following composition.

[0136] - Hydrophobic resin composition - 100 parts by mass of ethylene vinyl acetate resin (Tg -30°C to -25°C, MFR 8g / 10min to 10g / 10min, EVA, manufactured by Dow Mitsui Polychemicals Co., Ltd., Evaflex (registered trademark) P1007)

[0137] In the same manner as in Example 1-1, the major axis of the convex structure of specific film A was measured and found to be in the range of 0.49 μm to 1.27 μm, and the surface area was 10 μm. ２ It was confirmed that 18 convex structures were formed per square meter. The average height of the convex structures was measured in the same manner as in Example 1-1 and was found to be 128 nm.

[0138] In the same manner as in Example 1-1, the major axis of the recessed structure of specific film B was measured and found to be in the range of 0.46 μm to 1.22 μm. ２ It was confirmed that 23 recessed structures were formed per square meter. The average depth of the recessed structures was measured in the same manner as in Example 1-1 and was found to be 189 nm.

[0139] Example 1-7 A specific laminate, a specific film A, and a specific film B were produced in the same manner as in Example 1-5, except that the (meth)acrylic resin A in the hydrophilic resin composition was changed to (meth)acrylic resin B. The (meth)acrylic resin B was a propylene glycol monomethyl ether solution (solid concentration: 30.0% by mass) of a styrene / acrylic acid copolymer (monomer content: 71% by mass / 29% by mass, Mw: 8000, Tg: 102°C, acid value: 225 mgKOH / g).

[0140] In the same manner as in Example 1-1, the major axis of the convex structure of specific film A was measured and found to be in the range of 0.53 μm to 1.25 μm, and the surface area was 10 μm. ２ It was confirmed that 1.8 convex structures were formed per square meter. The average height of the convex structures was measured in the same manner as in Example 1-1 and was found to be 469 nm.

[0141] In the same manner as in Example 1-1, the major axis of the recessed structure of specific film B was measured and found to be in the range of 0.26 μm to 1.38 μm. ２It was confirmed that 1.9 recessed structures were formed per square meter. The average depth of the recessed structures was measured in the same manner as in Example 1-1 and was found to be 688 nm.

[0142] Example 1-8 A specific laminate, a specific film A, and a specific film B were produced in the same manner as in Example 1-5, except that the (meth)acrylic resin A in the hydrophilic resin composition was changed to (meth)acrylic resin C. The (meth)acrylic resin C was a propylene glycol monomethyl ether solution (solid concentration: 30.0% by mass) of a styrene / acrylic acid copolymer (monomer content: 71% by mass / 29% by mass, Mw: 13,000, Tg: 102°C, acid value: 225 mgKOH / g).

[0143] In the same manner as in Example 1-1, the major axis of the convex structure of specific film A was measured to be 0.26 μm to 0.30 μm, and the surface area was 10 μm. ２ It was confirmed that 44 convex structures were formed per square meter. The average height of the convex structures was measured in the same manner as in Example 1-1 and was found to be 198 nm.

[0144] In the same manner as in Example 1-1, the major axis of the recessed structure of specific film B was measured to be 0.32 μm to 0.85 μm, and the surface area was 10 μm. ２ It was confirmed that 45 recessed structures were formed per square meter. The average depth of the recessed structures was measured in the same manner as in Example 1-1 and was found to be 251 nm.

[0145] Example 1-9 A specific laminate, a specific film A, and a specific film B were produced in the same manner as in Example 1-5, except that the thickness of the hydrophilic resin layer was changed to 2.4 μm, the copper-plated PET film was changed to an adhesive tape (polyester adhesive tape No. 31B, manufactured by Nitto Denko Corporation), and no photosensitive resin layer was formed.

[0146] In the same manner as in Example 1-1, the major axis of the convex structure of specific film A was measured to be 0.42 μm to 1.72 μm, and the surface area was 10 μm. ２ It was confirmed that 15 convex structures were formed per square meter. The average height of the convex structures was measured in the same manner as in Example 1-1 and was found to be 106 nm.

[0147] In the same manner as in Example 1-1, the major axis of the recessed structure of specific film B was measured to be 0.44 μm to 1.15 μm, and the surface area was 10 μm. ２ It was confirmed that 16 recessed structures were formed per square meter. The average depth of the recessed structures was measured in the same manner as in Example 1-1 and was found to be 133 μm.

[0148] Example 1-10 A specific laminate, specific film A, and specific film B were produced in the same manner as in Example 1-5, except that the thickness of the hydrophilic resin layer was changed to 2.4 μm, the specific composition was changed to the following composition, and a photosensitive resin layer was not formed. Note that, because the specific composition contained only water and methanol, a water-soluble intermediate layer was not formed.

[0149] -Specific composition- Methanol 60.0 parts by mass Water 40.0 parts by mass

[0150] In the same manner as in Example 1-1, the major axis of the convex structure of specific film A was measured to be 0.37 μm to 1.12 μm, and the surface area was 10 μm. ２ It was confirmed that 28 convex structures were formed per square meter. The average height of the convex structures was measured in the same manner as in Example 1-1 and was found to be 168 nm.

[0151] In the same manner as in Example 1-1, the major axis of the recessed structure of specific film B was measured to be 0.14 μm to 1.12 μm, and the surface area was 10 μm. ２ It was confirmed that 26 recessed structures were formed per square meter. The average depth of the recessed structures was measured in the same manner as in Example 1-1 and was found to be 226 nm.

[0152] Example 1-11 A specific laminate, a specific film A, and a specific film B were produced in the same manner as in Example 1-10, except that the specific composition was changed to the following composition. Note that since the specific composition contained only methanol, no water-soluble intermediate layer was formed. -Specific composition- Methanol 100.0 parts by mass

[0153] In the same manner as in Example 1-1, the major axis of the convex structure of specific film A was measured to be 2.51 μm to 4.11 μm, and the surface area was 10 μm. ２It was confirmed that 1.4 convex structures were formed per square meter. The average height of the convex structures was measured in the same manner as in Example 1-1 and was found to be 20 nm.

[0154] In the same manner as in Example 1-1, the major axis of the recessed structure of specific film B was measured to be 2.01 μm to 4.19 μm, and the surface area was 10 μm. ２ It was confirmed that 1.9 recessed structures were formed per square meter. The average depth of the recessed structures was measured in the same manner as in Example 1-1 and was found to be 2035 nm.

[0155] Comparative Example 1-1 In the same manner as in Example 1-1, a hydrophobic resin layer having a thickness of 5 μm was formed on one surface of a PET film. The surface of the hydrophobic resin layer was observed in the same manner as in Example 1-1, but no convex or concave structure was formed.

[0156] Comparative Example 1-2 A laminate was produced in the same manner as in Example 1-1, except that a hydrophobic resin layer was not formed. The photosensitive resin layer of the laminate was laminated onto the copper foil side surface of a copper-plated PET film. The lamination conditions were a roll temperature of 100°C and a lamination speed of 4 m / min. After lamination onto the copper-plated PET film, the support and the film (hydrophilic resin layer) formed on the surface of the copper-plated PET film were peeled off at the interface between the hydrophilic resin layer of the specific laminate and the support. The surface of the film was observed in the same manner as in Example 1-1, and no convex or concave structure was formed.

[0157] Comparative Example 1-3 A laminate, a film A, and a film B were produced in the same manner as in Example 1-5, except that the specific composition was not used. The surfaces of the films A and B were observed in the same manner as in Example 1-1, but no convex structure or concave structure was formed.

[0158] <<Evaluation of Water Repellency>> At 25°C, the water contact angle of the surface on which the convex structure was formed of the specific film A obtained in the above example was measured in accordance with the sessile drop method of JIS R 3257 (1999), and the results are summarized in Table 1. Similarly, the water contact angle of the surface on which the concave structure was formed of the specific film B obtained in the above example was measured, and the results are summarized in Table 1. For Comparative Example 1-1, the water contact angle of the hydrophobic resin layer surface was measured, and the results are listed in Table 1. For Comparative Example 1-2, the water contact angle of the film surface was measured, and the results are listed in Table 1. For Comparative Example 1-3, the water contact angles of the surfaces of film A and film B were measured, and the results are listed in Table 1. In this evaluation, a water contact angle of 95° or more was considered to be good water repellency.

[0159] <<Measurement of Reflectance>> The reflectance when the surface of specific film A obtained in Example 1-4 on which the convex structures were formed was irradiated with light having a wavelength of 550 nm at an incident angle of 0° was measured using a spectrophotometer V-570 manufactured by JASCO Corporation, and the results are shown in Table 1. At this time, a black PET film with an adhesive layer (product name "Kukkiri Miel" manufactured by Tomoegawa Paper Co., Ltd.) was attached to the surface of the PET support opposite the surface on which the convex structures of specific film A were formed to prevent reflection, and the measurement was performed. The reflectance of the hydrophobic resin layer surface of Comparative Example 1-1 was also measured in the same manner as above, and the results are shown in Table 1.

[0160] <<Measurement of static friction coefficient>> The static friction coefficient of the surface on which the recessed structure of Specific Film B obtained in Examples 1-1 to 1-8 was formed against a glass substrate (blue plate (soda) glass, 200 mm x 200 mm x 5 mm thick) was measured in accordance with JIS K 7125 (1999) in an environment of 25°C and relative humidity of 50%, and the result is shown in Table 1. For Comparative Example 1-2, the static friction coefficient of the film was measured and shown in Table 1. For Comparative Example 1-3, the static friction coefficient of Film B was measured and shown in Table 1.

[0161]

[0162] Example 2-1 A 25 μm thick polyethylene terephthalate (PET) film was prepared as a support. The hydrophobic resin composition used in Example 1-1 was melt-extruded onto both sides of the support to form a 5 μm thick hydrophobic resin layer. Then, 16 μm thick polyethylene terephthalate (PET) films were attached to both sides of the hydrophobic resin layer as protective films.

[0163] The protective film on one side was peeled off, and the hydrophilic resin composition used in Example 1-1 was applied to the exposed surface of the hydrophobic resin layer, followed by drying in an oven at 80°C for 1 minute to form a hydrophilic resin layer with a thickness of 1.6 μm.

[0164] The specific composition used in Examples 1-4 was applied to the surface of the hydrophilic resin layer and dried in an oven at 80°C for 1 minute to obtain a specific laminate. ２ It was decided.

[0165] After the specific composition was applied and dried, the composition for forming a photosensitive resin layer used in Example 1-1 was applied to the surface of the hydrophilic resin layer, and dried in an oven at 80° for 1 minute to form a photosensitive resin layer having a thickness of 2.2 μm.

[0166] The photosensitive resin layer of the specific laminate was laminated onto the copper foil side surface of the copper-plated PET film under the conditions of a roll temperature of 100° C. and a lamination speed of 4 m / min.

[0167] The protective film on the other side was peeled off, and the hydrophilic resin composition used in Example 1-1 was applied to the exposed surface of the hydrophobic resin layer, followed by drying in an oven at 80°C for 1 minute to form a hydrophilic resin layer with a thickness of 1.6 μm.

[0168] The specific composition used in Examples 1-4 was applied to the surface of the hydrophilic resin layer and dried in an oven at 80°C for 1 minute to obtain a specific laminate. ２ It was decided.

[0169] After the specific composition was applied and dried, the composition for forming a photosensitive resin layer used in Example 1-1 was applied to the surface of the hydrophilic resin layer, and dried in an oven at 80° for 1 minute to form a photosensitive resin layer having a thickness of 2.2 μm.

[0170] The photosensitive resin layer of the obtained specific laminate was laminated onto the copper foil side surface of a copper-plated PET film. The lamination conditions were a roll temperature of 100°C and a lamination speed of 4 m / min. After lamination onto the copper-plated PET film, the hydrophilic and hydrophobic resin layers of the specific laminate were peeled off at the interface to obtain a specific film A (hydrophobic resin layer) having a convex structure formed on both sides of the support, and a specific film B (hydrophilic resin layer) having a concave structure formed on the surface of the copper-plated PET film. Hereinafter, a laminate of the support and the specific film A formed on both sides of the support will be referred to as a supported film.

[0171] In the same manner as in Example 1-1, the major axis of the convex structure of specific film A was measured to be 0.08 μm to 0.24 μm, and the surface area was 10 μm. ２ It was confirmed that 269 convex structures were formed per unit area. The average height of the convex structures was measured in the same manner as in Example 1-1 and was found to be 355 μm. The water contact angle of the surface of specific film A on which the convex structures were formed was measured in the same manner as in Example 1-1 and was found to be 140°.

[0172] In the same manner as in Example 1-1, the major axis of the recessed structure of specific film B was measured to be 0.08 μm to 0.29 μm, and the surface area was 10 μm. ２ It was confirmed that 400 recessed structures were formed per unit area. The average depth of the recessed structures was measured in the same manner as in Example 1-1 and was found to be 126 μm. The water contact angle of the surface of Specific Film B on which the recessed structures were formed was measured in the same manner as in Example 1-1 and was found to be 120°.

[0173] <<Measurement of Transmittance>> The transmittance of a supported film comprising the support obtained in Example 2-1 and specific film A having convex structures formed on both sides thereof, when irradiated with light having a wavelength of 550 nm at an incident angle of 0°, was measured using an ultraviolet-visible spectrophotometer UV-1800 manufactured by Shimadzu Corporation, and is shown in Table 2. The transmittance of the hydrophobic resin layer surface of Comparative Example 1-1 was also measured in the same manner as above, and is shown in Table 1.

[0174]

[0175] Tables 1 and 2 show that the specific film A and specific film B obtained from the laminates produced in the examples have higher water contact angles and better water repellency than the films produced in the comparative examples. Table 1 shows that the specific film A obtained from the laminate produced in Example 1-4 has better antireflection properties than the hydrophobic resin layer produced in Comparative Example 1-1. Table 1 shows that the specific film B obtained from the laminates produced in Examples 1-1 to 1-8 has a lower static friction coefficient against glass and better slip resistance than the films produced in Comparative Examples 1-2 and 1-3. Table 2 shows that the supported film obtained from the laminate produced in Example 2-1 has better antireflection properties than the hydrophobic resin layer produced in Comparative Example 1-1.

[0176] The disclosure of Japanese Patent Application No. 2022-061220, filed on March 31, 2022, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A step of forming a hydrophobic resin layer containing a hydrophobic resin on a surface of a support; forming a hydrophilic resin layer containing a hydrophilic resin on a surface of the hydrophobic resin layer; applying a composition containing an alcohol to a surface of the hydrophilic resin layer, followed by drying to form a convex structure on the hydrophilic resin layer side surface of the hydrophobic resin layer and a concave structure on the hydrophobic resin layer side surface of the hydrophilic resin layer; A method for producing a laminate, comprising:

2. The method for producing a laminate according to claim 1 , wherein the support has a total light transmittance of 50% or more.

3. The method for producing a laminate according to claim 1 or 2, wherein the support contains a polyester resin.

4. The method for producing a laminate according to claim 1 or 2, wherein the hydrophobic resin has a glass transition temperature lower than a glass transition temperature of the hydrophilic resin.

5. The method for producing a laminate according to claim 1 or 2, wherein the hydrophobic resin is a polyolefin resin.

6. The method for producing a laminate according to claim 1 or 2, wherein the hydrophilic resin is a (meth)acrylic resin.

7. The method for producing a laminate according to claim 1 or 2, wherein the composition further contains water.

8. A step of producing a laminate by the method of producing a laminate according to claim 1; and peeling the hydrophobic resin layer and the hydrophilic resin layer of the laminate at an interface therebetween.

9. A film containing a hydrophobic resin, At least one surface has a convex structure having a major axis of 0.02 μm to 5 μm and an average height of 10 nm to 3000 nm; and The convex structure is formed on the surface of ２ A film in which 1 to 1000 pieces are formed per film.

10. The film according to claim 9 , wherein the surface on which the convex structures are formed has a water contact angle of 100° or more at 25° C.

11. The film according to claim 9 or 10, wherein the reflectance when the surface on which the convex structure is formed is irradiated with light having a wavelength of 550 nm is 4% or less.

12. A support and the film according to claim 9 or 10 provided on one surface of the support, A film with a support, wherein the surface of the film opposite to the surface on which the convex structure is formed is in contact with the support.

13. The film is provided on both sides of the support, and The supported film according to claim 12, which has a transmittance of 92% or more for light having a wavelength of 550 nm.

14. A film containing a hydrophilic resin, At least one surface has a concave structure with a major axis of 0.02 μm to 5 μm and an average depth of 10 nm to 3000 nm; and The recessed structure is formed on the surface of ２ A film in which 1 to 1000 pieces are formed per film.

15. The film according to claim 14, wherein the surface on which the recessed structure is formed has a water contact angle of 95° or more at 25°C.

16. A support, a hydrophobic resin layer, a hydrophilic resin layer, a water-soluble intermediate layer, and a photosensitive resin layer, in this order; the hydrophobic resin layer contains a polyolefin resin, the hydrophilic resin layer contains a (meth)acrylic resin, The water-soluble intermediate layer contains a water-soluble resin, The hydrophobic resin layer and the hydrophilic resin layer are peelable at the interface therebetween, The hydrophilic resin layer has a 10 μm thick layer on the surface of the hydrophobic resin layer. ２ 1 to 1000 recessed structures are formed per unit area. The recessed structure has a major axis of 0.02 μm to 5 μm and an average depth of 10 nm to 3000 nm, and The photosensitive transfer material has a surface having a static friction coefficient against glass of 1.50 or less.