Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
  • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
  • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
  • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
  • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/06—Interconnection of layers permitting easy separation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets

Definitions

• the present disclosure relates to a method for producing a laminate, a method for producing a film, a film, a film with a support, and a photosensitive transfer material.
• Water-repellent films having at least one of a fine concave structure and a fine convex structure on the surface are manufactured by various methods. For example, a method of stretching a film obtained by forming a composition containing a resin and particles, 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 composition. etc. are known.
• the water-repellent film produced may have insufficient functionality such as water repellency.
• a 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 a high manufacturing cost.
• a problem to be solved by an embodiment of the present disclosure is to provide a method for manufacturing a laminate and a method for manufacturing a film that are simple and capable of manufacturing a film with excellent functionality. Moreover, the problem to be solved by an embodiment of the present disclosure is to provide a film, a support-attached film, and a photosensitive transfer material that can be manufactured by a simple method and have excellent functionality.
• ⁇ 1> Forming a hydrophobic resin layer containing a hydrophobic resin on the surface of the support, forming a hydrophilic resin layer containing a hydrophilic resin on the surface of the hydrophobic resin layer; A composition containing alcohol is coated on the surface of the hydrophilic resin layer and dried, and a convex structure is formed on the surface of the hydrophobic resin layer on the hydrophilic resin layer side. forming a concave structure on the surface;
• a method for manufacturing a laminate including: ⁇ 2> The method for producing a laminate according to ⁇ 1> above, wherein the support has a total light transmittance of 50% or more.
• ⁇ 3> The method for producing a laminate according to ⁇ 1> or ⁇ 2> above, wherein the support contains a polyester resin.
• ⁇ 4> The method for producing a laminate according to any one of ⁇ 1> to ⁇ 3> above, wherein the hydrophobic resin has a glass transition temperature lower than the glass transition temperature of the hydrophilic resin.
• ⁇ 5> The method for producing a 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.
• ⁇ 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 surface on which the convex structure is formed has a reflectance of 4% or less when irradiated with light at a wavelength of 550 nm.
• ⁇ 12> Comprising a support and the film according to any one of ⁇ 9> to ⁇ 11> above provided on one surface of the support, A film with a support, wherein a surface of the film opposite to the surface on which the convex structure is formed is in contact with the support.
• ⁇ 16> Comprising 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 (meth)acrylic resin
• the water-soluble intermediate layer contains a water-soluble resin, Peelable at the interface between the hydrophobic resin layer and the hydrophilic resin layer
• the hydrophilic resin layer has 1 to 1000 concave structures formed per 10 ⁇ m 2 on the surface of the hydrophobic resin layer
• a photosensitive transfer material wherein the concave structure has a major axis of 0.02 ⁇ m to 5 ⁇ m, an average depth of 10 nm to 3000 nm, and a coefficient of static friction of the surface with respect to glass of 1.50 or less.
• a method for producing a laminate and a method for producing a film that are simple and can produce a film with excellent functionality. Further, according to an embodiment of the present disclosure, it is possible to provide a film, a support-attached film, and a photosensitive transfer material that can be manufactured by a simple method and have excellent functionality.
• FIG. 1 shows a SEM image (30,000x magnification) of the surface of the specific film A produced in Example 1-1 on which the convex structure was formed.
• FIG. 2 shows a SEM image (30,000x magnification) of the surface of the specific film B produced in Example 1-1 on which the concave structure was formed.
• FIG. 3 shows a SEM image (magnification: 30,000 times) of the surface of the specific film A produced in Example 1-4 on which the convex structure was formed.
• FIG. 4 shows a SEM image (30,000x magnification) of the surface of the specific film B produced in Example 1-4 on which the concave structure was formed.
• a numerical range expressed using “ ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
• the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step.
• the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.
• the term “process” includes not only an independent process but also a process that is not clearly distinguishable from other processes, as long as the intended purpose of the process is achieved. .
• (meth)acrylic means both acrylic and methacrylic, or either one.
• the amount of each component in the composition, etc. means the total amount of the multiple substances present in the composition, etc., unless otherwise specified.
• a combination of two or more preferred aspects or forms is a more preferred aspect or form.
• hydrophilic resin means a resin having a polar group.
• hydrophobic resin means a resin that does not have a polar group.
• Examples of the polar group include a hydroxyl group, a carboxy group, a sulfonic acid group, a phosphoric acid group, an amide group, an imide group, and the like, and a carboxy group is preferable from the viewpoint of water repellency.
• 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 (hereinafter referred to as a step of forming a hydrophobic resin layer); A step of 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); A composition containing alcohol (hereinafter referred to as a specific composition) is applied to the surface of the hydrophilic resin layer and dried, and a convex structure is formed on the surface of the hydrophilic resin layer on the hydrophilic resin layer side.
• a step of forming a concave structure on the surface of the plastic layer side hereinafter referred to as a step of forming a convex structure and a concave structure
• 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. Further, as described below, when a water-soluble intermediate layer is formed using a specific composition, the method for producing a laminate of the present disclosure includes a step of forming a photosensitive resin layer on the surface of the water-soluble intermediate layer. Good too.
• the above two types of steps will be collectively referred to as the step of forming a photosensitive resin layer.
• the method for manufacturing 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 resins. It is preferable that the hydrophobic resin does not dissolve 0.1% by mass or more in water (25°C, pH 7) or methanol (25°C).
• hydrophobic resin examples include polyolefin resin, polystyrene resin, polyester resin, (meth)acrylate resin, and the like.
• polyolefin resins are preferred, polyethylene, polypropylene, or ethylene vinyl acetate resins are more preferred, and polyethylene is even more preferred, from the viewpoint of water repellency, antireflection properties, and the like.
• 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.
• HDPE is polyethylene with a density of 0.945 g/cm 3 or more
• MDPE is polyethylene with a density of 0.925 g/cm 3 or more and less than 0.945 g/cm 3
• LDPE and LLDPE are polyethylene with a density of 0.925 g/cm 3 or more.
• cm3 means less than polyethylene.
• 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. It is 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 more preferably -100°C to 0°C.
• the glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), and more specifically, the glass transition temperature of JIS K 7121 (1987) "Method for measuring the transition temperature of plastics". It is determined by the "extrapolated glass transition start temperature" described in the method of determination.
• DSC differential scanning calorimetry
• the mass melt flow rate (MFR) of the hydrophobic resin is preferably 0.1 g/10 min to 100 g/10 min, and 0.3 g/10 min to 30 g/10 min. is more preferable, and even more preferably 2 g/10 min to 20 g/10 min.
• the mass melt flow rate is determined by an extrusion blast meter (capillary rheometer), and more specifically, JIS K7210-1 "Melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastics-thermoplastics”. ) is determined using the method described in ⁇ How to determine
• the content of the hydrophobic resin with respect to the total mass of the hydrophobic resin layer is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass. % or more, and may be 100% by mass.
• the hydrophobic resin layer contains additives such as surfactants, pigments, dyes, ultraviolet absorbers, light stabilizers, antioxidants, rust preventives, adhesion promoters, thermal polymerization inhibitors, and inorganic particles. Good too.
• the thickness of the hydrophobic resin is preferably 1 ⁇ m to 20 ⁇ m, more preferably 3 ⁇ m to 15 ⁇ m, and even more preferably 5 ⁇ m to 10 ⁇ m.
• the method for forming the hydrophobic resin layer on the surface of the support is not particularly limited, and examples include a method of applying a hydrophobic resin composition containing the above-described hydrophobic resin and the like onto the surface of the support and drying it.
• the hydrophobic resin composition may contain an organic solvent.
• the support may contain one or more resins, and examples of the resins include polyester resins, polyolefin resins, (meth)acrylic resins, polyamide resins, polyimide resins, and polyamideimide resins.
• the support preferably contains polyester resin, and more preferably contains polyethylene terephthalate.
• the content of the resin based on 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 100% by mass. Good too.
• the support may contain the above additives.
• the total light transmittance of the support is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more.
• the total light transmittance is measured in accordance with the method specified in JIS K 7375 (2008).
• the support is preferably a film containing the above resin, and more preferably a biaxially stretched film from the viewpoint of mechanical strength and solvent resistance.
• the thickness of the support is preferably 1 ⁇ m to 50 ⁇ m, more preferably 10 ⁇ m to 40 ⁇ m, and even more preferably 15 ⁇ m to 30 ⁇ m.
• the method for manufacturing a laminate of the present disclosure includes a step of forming a hydrophilic resin layer containing a hydrophilic resin on the surface of the hydrophobic resin layer.
• the hydrophilic resin layer may contain two or more types of hydrophilic resins.
• the hydrophilic resin is preferably dissolved in water (25° C., pH 7) or methanol (25° C.) in an amount of 0.1% by mass or more.
• hydrophilic resin examples include (meth)acrylic resin, styrene (meth)acrylic resin, epoxy resin, polyurethane resin, nylon resin, butyral resin, vinyl alcohol resin, polyvinylpyrrolidone resin, and cellulose resin.
• (meth)acrylic resin is preferred from the viewpoint of water repellency.
• (meth)acrylic resin is preferable from the viewpoint of lowering the coefficient of static friction with respect to glass.
• the laminate manufactured by the manufacturing method of the present disclosure includes a photosensitive resin layer, the interface between the hydrophobic resin layer and the hydrophilic resin layer is peeled off by lowering the coefficient of static friction of the hydrophilic resin layer with respect to glass.
• slipperiness hereinafter also simply referred to as slipperiness
• the exposure of the photosensitive resin layer can be improved. can be performed well.
• the hydrophilic resin includes a structural unit having a polar group.
• the content of the structural unit having a polar group with respect to the total amount of all structural units contained in the hydrophilic resin is preferably 10% by mass to 40% by mass, and 13% by mass. It is more preferably from 15% to 35% by weight, and even more preferably from 15% to 35% by weight.
• the structural unit having a polar group is preferably a structural unit corresponding to (meth)acrylic acid.
• the acid value of the hydrophilic resin is preferably 150 mgKOH/g or more, and more preferably 150 mgKOH/g to 300 mgKOH/g.
• the acid value is measured according to the method described in JIS K0070 (1992).
• the glass transition temperature of the hydrophilic resin is preferably 30°C or higher, more preferably 50°C to 180°C, and even more preferably 90°C to 150°C. preferable.
• 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.
• GPC gel permeation chromatography
• the content of the hydrophilic resin with respect to the total mass of the hydrophilic resin layer is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass. It is more preferable that the amount is above, and may be 100% by mass.
• the hydrophilic resin layer may contain the above additives.
• the thickness of the hydrophilic resin is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m to 10 ⁇ m, and even more preferably 1 ⁇ m to 5 ⁇ m.
• the method of forming the hydrophilic resin layer on the surface of the hydrophobic resin layer is not particularly limited, and examples include a method of applying a hydrophilic resin composition containing the above-mentioned hydrophilic resin etc. to the surface of the support and drying it. It will be done.
• the hydrophilic resin composition may contain an organic solvent.
• the method for producing a laminate of the present disclosure includes coating a specific composition on the surface of a hydrophilic resin layer, drying it, and forming a convex structure on the surface of the hydrophilic resin layer on the hydrophilic resin layer side. It includes a step of forming a concave structure on the layer side surface.
• a concave structure is formed on the surface of the hydrophilic resin layer on the hydrophobic resin layer side.
• the specific composition that became a gas is gradually absorbed into the hydrophilic resin layer, and the area where the foamed gas was present becomes a vacuum space, and the specific composition volatilizes outside the system, resulting in a hydrophilic resin layer. Since the hydrophobic resin layer is attracted toward the space of the hydrophilic resin layer that is sufficiently harder than the hydrophobic resin layer, a convex structure is formed on the surface of the hydrophobic resin layer on the hydrophilic resin layer side. It is estimated to be.
• the protrusions of the hydrophobic resin layer that have penetrated the hydrophilic resin layer may be stretched and may be transformed into protrusions with a high aspect ratio. It is estimated to be.
• the convex structure imparts excellent functionality such as water repellency and anti-reflection properties to the surface of the hydrophobic resin layer, and the concave structure imparts excellent functionality such as water repellency and slipperiness to the surface of the hydrophilic resin layer. It is estimated that The water repellency can be explained as a lotus leaf effect, and the anti-reflection property can be explained as a moth-eye effect.
• the specific composition contains alcohol.
• the specific composition may contain two or more types of alcohol.
• examples of the alcohol include methanol, ethanol, propanol, butanol, and the like, with methanol being preferred from the viewpoints of water repellency, antireflection properties, slipperiness, and the like.
• the content of alcohol based on the total mass of the specific composition is preferably 30% by mass to 70% by mass, and preferably 40% by mass to 65% by mass. is more preferable, and even more preferably 45% by mass to 60% by mass.
• the specific composition contains water.
• the ratio of the water content to the alcohol content is 1/ from the viewpoint of water repellency, antireflection properties, slipperiness, etc.
• the ratio is preferably 9 to 5/5, more preferably 2/8 to 4/6, and even more preferably 2/8 to 3/7.
• compositions may contain water-soluble resins.
• the specific composition contains a water-soluble resin
• the above-mentioned convex structure and concave structure 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 types of water-soluble resins.
• the water-soluble resin refers to a resin that dissolves 1 g or more in 100 g of water with a pH of 7.0 at 23°C. It is preferable that the water-soluble resin has the above polar group.
• water-soluble resins examples include polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), water-soluble polysaccharides (methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, propylmethylcellulose, etc.), pullulan, Examples include starch (hydroxypropyl starch, carboxymethyl starch, etc.), chitosan, cyclodextrin), polyethylene oxide, polyethyloxazoline, methylolmelamine, polyacrylamide, phenolic resin, and the like.
• PVP polyvinylpyrrolidone
• PVA polyvinyl alcohol
• water-soluble polysaccharides methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, propylmethylcellulose, etc.
• pullulan examples include starch (hydroxypropyl star
• 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, and preferably 2% to 13% by mass. It is more preferable that the amount is 3% by mass to 10% by mass.
• compositions may contain water-insoluble resins.
• the above-mentioned convex structure and concave structure 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 types of water-soluble resins.
• a water-insoluble resin refers to a resin that dissolves less than 1 g in 100 g of water with a pH of 7.0 at 23°C.
• water-insoluble resins examples include styrene particle aqueous dispersion, methyl methacrylate aqueous dispersion, acrylic resin aqueous dispersion, polyolefin resin aqueous dispersion, polyester resin aqueous dispersion, polyurethane resin aqueous dispersion, epoxy resin aqueous dispersion, etc. can be mentioned.
• 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, and 2% by mass to 13% by mass. More preferably, it is 3% by mass to 10% by mass.
• the specific composition may contain the above additives. Moreover, the specific composition may contain an organic solvent other than alcohol.
• the amount of the specific composition applied is preferably 10 mL/m 2 to 45 mL/m 2 , and preferably 15 mL/m 2 to 40 mL/m 2 . More preferably, it is 20 mL/m 2 to 30 mL/m 2 .
• the thickness of the water-soluble intermediate layer is preferably 0.01 ⁇ m to 10 ⁇ m, from the viewpoint of water repellency, antireflection properties, slipperiness, etc. More preferably, the thickness is 1 ⁇ m to 2 ⁇ m.
• the drying temperature of the specific composition is preferably 50°C to 100°C, more preferably 60°C to 90°C.
• drying temperature refers to the temperature of the environment in which a particular composition is dried, and does not mean the temperature of the particular composition.
• the method for producing a laminate of the present disclosure includes a step of coating and drying a specific composition, and then forming a photosensitive resin layer on the surface of a hydrophilic resin layer;
• the method for manufacturing a laminate of the present disclosure may include a step of forming a photosensitive resin layer on the surface of the hydrophilic resin layer.
• the photosensitive resin layer may be a negative photosensitive resin layer or a positive photosensitive resin layer.
• the photosensitive resin layer can contain one or more polymers having acid groups (hereinafter also simply referred to as polymers).
• the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group.
• the acid group is a carboxy group.
• 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 reactive groups.
• a polymerizable group is preferable. Examples of the polymerizable group include ethylenically unsaturated groups, polycondensable groups (hydroxy groups, carboxy groups, etc.), polyaddition reactive groups (epoxy groups, isocyanate groups, etc.).
• the acid value of the polymer is preferably 60 mgKOH/g to 200 mgKOH/g, more preferably 100 mgKOH/g to 200 mgKOH/g, and 150 mgKOH/g to 200 mgKOH/g. It is particularly preferable.
• 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.
• the polymer may have structural units derived from non-acidic monomers.
• non-acidic monomers include (meth)acrylic acid esters, vinyl alcohol ester compounds, (meth)acrylonitrile, and aromatic vinyl compounds.
• (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, benzyl (meth)acrylate, and the like.
• vinyl alcohol ester compounds include vinyl acetate.
• aromatic vinyl compounds include styrene and styrene derivatives.
• the non-acidic monomer is one or more monomers selected from the group consisting of methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, styrene derivatives, and benzyl (meth)acrylate.
• the content of the polymer is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, based on the total mass of the photosensitive resin layer. , more preferably 30% by mass to 70% by mass.
• the photosensitive resin layer may contain one or more kinds of polymerizable compounds.
• the polymerizable compound is not limited, and any known polymerizable compound can be used.
• the polymerizable compound is an ethylenically unsaturated compound.
• Ethylenically unsaturated compounds are compounds that have one or more ethylenically unsaturated groups.
• the ethylenically unsaturated group is preferably a (meth)acryloyl group.
• the ethylenically unsaturated compound is a (meth)acrylate compound.
• an ethylenically unsaturated compound having a bisphenol structure is also suitably used.
• Examples of the ethylenically unsaturated compound having a bisphenol structure include alkylene oxide-modified bisphenol A di(meth)acrylate.
• the alkylene oxide-modified bisphenol A di(meth)acrylate includes ethylene glycol dimethacrylate, which has an average of 5 moles of ethylene oxide added to each end of bisphenol A, and bisphenol A with an average of 2 moles of ethylene oxide added to each end of the bisphenol A.
• Examples include dimethacrylate of glycol and dimethacrylate of alkylene glycol in which an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide are added to both ends of bisphenol A.
• alkylene oxide-modified bisphenol A di(meth)acrylate include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane, 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl) Examples include propane.
• 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.
• 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 3000, more preferably 280 to 2200, and 300 to 2200. It is particularly preferable that
• 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, based on the total mass of the photosensitive resin layer.
• the photosensitive resin layer can contain a polymerization initiator.
• a polymerization initiator conventionally known photoradical polymerization initiators can be used.
• the content of the polymerization initiator with respect to the total mass of the photosensitive resin layer is not particularly limited, and can be 0.01% by mass to 1% by mass.
• the photosensitive resin layer may contain the above additives.
• the thickness of the photosensitive resin layer is not particularly limited, and can be 0.5 ⁇ m to 5 ⁇ m.
• the method for forming the photosensitive resin layer is not particularly limited, and includes applying a composition for forming a photosensitive resin layer containing the above photosensitive resin etc. to the surface of the hydrophilic resin layer or the surface of the water-soluble intermediate layer. , drying method, etc.
• the composition for forming a photosensitive resin layer may contain an organic solvent. From the viewpoints of water repellency, antireflection properties, slipperiness, etc., the content of alcohol based on the total mass of the composition for forming a photosensitive resin layer is preferably 50% by mass or less, and preferably 10% by mass or less. More preferred.
• the content of water relative to the total mass of the composition for forming a photosensitive resin layer is preferably 5% by mass or less, and preferably 1% by mass or less. It is more preferable, and it is particularly preferable not to contain it.
• the method for manufacturing a film of the present disclosure includes a step of manufacturing a laminate by the method for manufacturing a laminate (hereinafter referred to as a step of manufacturing a laminate); a step of peeling off at the interface between the hydrophobic resin layer and the hydrophilic resin layer of the laminate (hereinafter referred to as the peeling step); including.
• a film consisting of a hydrophobic resin layer on the surface of the support and having a convex structure on the surface hereinafter referred to as specific film A
• specific film B a hydrophilic resin layer having a concave structure on the surface.
• the method for manufacturing a film of the present disclosure includes a step of peeling at an interface between a hydrophobic resin layer and a hydrophilic resin layer included in the laminate.
• the peeling method is not particularly limited, and may be performed manually or with a peeling device.
• the peeling force of the hydrophobic resin layer and the hydrophilic resin layer is 0.5 g/ It is preferably from cm to 50 g/cm, more preferably from 0.5 g/cm to 10 g/cm.
• the peeling force is measured by using a testing machine as the peeling force when a hydrophobic resin layer is peeled from a hydrophilic resin layer in a 180° direction at a speed of 300 mm/min in a 25° C. environment.
• the long axis of the convex structure on the surface of specific film A is preferably 0.02 ⁇ m to 5 ⁇ m, more preferably 0.02 ⁇ m to 1 ⁇ m, and 0.02 ⁇ m to 0.0 ⁇ m. More preferably, the thickness is .4 ⁇ m.
• the long axis of the convex structure is determined as follows. First, a SEM image of the surface of the film on which the convex structure is formed is obtained using a scanning electron microscope (SEM). On the convex structure of the SEM image, the distance between two points with the maximum distance is measured, and this is defined as the major axis of the convex structure.
• the average height of the convex structures on the surface of the specific film A is preferably 10 nm to 3000 nm, more preferably 30 nm to 1000 nm, and preferably 100 nm to 500 nm. More preferred.
• the average height of the convex structure 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 convex structures in the SEM image are arbitrarily selected, the maximum height difference is measured as the height, and the average is determined, which is taken as the average height of the convex structures.
• the number of convex structures is measured from a SEM image of the surface of the film on which the convex structures are formed.
• the water contact angle of the surface of the specific film A on which the convex structure is formed is preferably 100° or more, more preferably 105° or more, and 110° or more from the viewpoint of water repellency. It is even more preferable that there be.
• the water contact angle is measured in accordance with the sessile drop method of JIS R 3257 (1999).
• the reflectance when the surface of the specific film A on which the convex structure is formed is irradiated with light with a wavelength of 550 nm is preferably 4% or less, and preferably 3% or less. More preferred. Note that the incident angle of light is 0°.
• the major axis of the concave structure in specific film B is preferably 0.02 ⁇ m to 5 ⁇ m, more preferably 0.02 ⁇ m to 1 ⁇ m, and 0.02 ⁇ m to 0.4 ⁇ m. It is even more preferable that there be.
• the major axis of the concave structure is determined as follows. First, a SEM image of the surface of the film on which the concave structure is formed is obtained using a scanning electron microscope (SEM). On the concave structure of the SEM image, the distance between two points with the maximum distance is measured, and this is defined as the major axis of the convex structure.
• the average depth of the concave structure in specific film B is preferably 10 nm to 3000 nm, more preferably 30 nm to 1000 nm, even more preferably 100 nm to 500 nm. .
• the average depth of the concave structure 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 concave structures in the SEM image are arbitrarily selected, the maximum height difference is measured as the depth, and the average thereof is determined to be the average depth of the concave structures.
• the number of concave structures is measured from a SEM image of the surface of the film on which the concave structures are formed.
• the water contact angle of the surface of the specific film B on which the concave structure is formed is preferably 95° or more, more preferably 105° or more, and 110° or more from the viewpoint of water repellency. It is even more preferable that there be.
• the coefficient of static friction of the surface of the specific film B on which the concave structure is formed with respect to glass is preferably 1.50 or less, more preferably 1.00 or less, and 0.85 or less. It is even more preferable that there be.
• the lower limit of the static friction coefficient is not particularly limited, and can be set to 0.1 or more. In the present disclosure, the static friction coefficient is measured in an environment of 25° C. and 50% relative humidity in accordance with JIS K 7125 (1999).
• the film of the present disclosure contains a hydrophobic resin, At least one surface has a convex structure with a major axis of 0.02 ⁇ m to 5 ⁇ m and an average height of 10 nm to 3000 nm, and 1 to 1000 convex structures are formed per 10 ⁇ m 2 of the surface.
• the content of the hydrophobic resin relative to the total mass of the film is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. It is more preferable that the amount is 100% by mass.
• the film may contain a surfactant and the above additives.
• the long axis of the convex structure is preferably 0.02 ⁇ m to 5 ⁇ m, more preferably 0.02 ⁇ m to 1 ⁇ m, and 0.02 ⁇ m to 0.4 ⁇ m. is even more preferable.
• the long axis of the convex structure is measured by the same method as described above.
• the average height of the convex structure is preferably 30 nm to 1000 nm, more preferably 100 nm to 500 nm.
• the average height of the convex structure is measured by the same method as described above.
• 10 to 900 convex structures are formed per 10 ⁇ m 2 of the surface, and more preferably 30 to 850 convex structures are formed.
• the water contact angle of the surface of the film on which the convex structure is formed is preferably 100° or more, more preferably 105° or more, and 110° or more from the viewpoint of water repellency. is even more preferable.
• the number of convex structures is measured by the same method as described above.
• the reflectance when the surface of the film on which the convex structure is formed is irradiated with light with a wavelength of 550 nm is preferably 4% or less, more preferably 3% or less.
• the incident angle of light is 0°.
• the thickness of the film is preferably 1 ⁇ m to 20 ⁇ m, more preferably 3 ⁇ m to 15 ⁇ m, and even more preferably 5 ⁇ m to 10 ⁇ m.
• Applications of the film of the present disclosure include water repellent films, antifouling films, highly transparent films, antireflection films, and the like.
• the film of the present disclosure can be manufactured by the above-described film manufacturing method.
• the film with a support of the present disclosure includes a support and a film having the convex structure provided on one surface of the support, The surface of the film having a convex structure that is opposite to the surface on which the convex structure is formed is in contact with the support. Since the film and support having a convex structure have been described above, their description is omitted here.
• the film with a support of the present disclosure has a film having a convex structure on both sides of the support, and has a transmittance of 92% or more for light at a wavelength of 550 nm. If the convex structure is only on one side, the effect of improving the transparency of the film due to antireflection is only half of the effect, and the effect of improving the transmittance is halved due to reflection from the non-reflection-prevented surface without the convex structure. It is preferable that films having the following properties are provided on both sides of the support. It is more preferable that the light transmittance is 94% or more. Note that the incident angle of light is 0°.
• Applications of the film with a support of the present disclosure include water-repellent films, antifouling films, highly transparent films, antireflection films, and the like.
• the film of the present disclosure contains a hydrophilic resin, At least one surface has a concave structure with a major axis of 0.02 ⁇ m to 5 ⁇ m and an average depth of 10 nm to 3000 nm, and 1 to 1000 concave structures are formed per 10 ⁇ m 2 of the surface.
• the content of the hydrophilic resin with respect to the total mass of the film is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. It is even more preferable that the amount is 100% by mass.
• the film may contain the above additives.
• the long axis of the concave structure is preferably 0.02 ⁇ m to 5 ⁇ m, more preferably 0.02 ⁇ m to 1 ⁇ m, and preferably 0.02 ⁇ m to 0.4 ⁇ m. More preferred.
• the long axis of the concave structure is measured by the same method as described above.
• the average depth of the concave structure is preferably 30 nm to 1000 nm, more preferably 100 nm to 500 nm.
• the average depth of the concave structure is measured by the same method as described above.
• the water contact angle of the surface of the film with the concave structure formed thereon is preferably 95° or more, more preferably 105° or more, and 110° or more from the viewpoint of water repellency. is even more preferable.
• the water contact angle is measured by the same method as described above.
• the coefficient of static friction of the surface of the film of the present disclosure on which the concave structure is formed with respect to glass is preferably 1.50 or less, more preferably 1.00 or less, and 0.85 or less. It is more preferable that The lower limit of the static friction coefficient is not particularly limited, and can be set to 0.1 or more.
• the static friction coefficient is measured by the same method as described above.
• Applications of the film of the present disclosure include water-repellent films, antifouling films, slippery films, surface films of photosensitive transfer materials, and the like.
• the film of the present disclosure can be manufactured by the above-described film manufacturing method.
• the photosensitive transfer material of the present disclosure includes 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 (meth)acrylic resin, the water-soluble intermediate layer contains a water-soluble resin, It can be peeled off at the interface between the hydrophobic resin layer and the hydrophilic resin layer, The hydrophilic resin layer has a concave structure of 1 to 1000 concave structures per 10 ⁇ m2 on the surface of the hydrophobic resin layer, The concave structure has a long axis of 0.02 ⁇ m to 5 ⁇ m, an average depth of 10 nm to 3000 nm, and a coefficient of static friction of the surface with respect to glass of 1.50 or less.
• the support, hydrophobic resin layer, hydrophilic resin layer, water-soluble intermediate layer, and photosensitive resin layer included in the photosensitive transfer material of the present disclosure are as described above, and their descriptions are omitted here.
• the preferable numerical ranges of the number, major axis, and average depth of the concave structures included in the hydrophilic resin layer are also as described above, and description thereof will be omitted here.
• the preferable numerical range of the coefficient of static friction of the surface of the hydrophilic resin layer with the concave structure formed with respect to the glass is also as described above, and the description thereof will be omitted here.
• the hydrophobic resin layer may have a convex structure formed on the surface on the hydrophilic resin layer side.
• the preferable numerical ranges for the number, major axis, and average depth of the convex structures are also as described above, and their description is omitted here.
• the water contact angle of the surface on which the convex structure of the hydrophobic resin layer is formed and the preferable numerical range of the reflectance when irradiated with light with a wavelength of 550 nm are also as described above, and their description is omitted here.
• the photosensitive transfer material of the present disclosure can be peeled off at the interface between the hydrophobic resin layer and the hydrophilic resin layer. Thereby, it becomes possible to transfer the transfer layer including the hydrophilic resin layer, the water-soluble intermediate layer, and the photosensitive resin layer in this order onto the surface of the object to be transferred.
• the preferable numerical ranges of the peeling forces of the hydrophobic resin layer and the hydrophilic resin layer are also as described above, and their description is omitted here.
• the film of the present disclosure can be manufactured by the method for manufacturing a laminate described above.
• Example 1-1 A 25 ⁇ m thick polyethylene terephthalate (PET) film (total light transmittance 91%, biaxially stretched film) was prepared as a support. On one surface of the support, a hydrophobic resin composition having the following composition was melt-extruded to form a hydrophobic resin layer with a thickness of 5 ⁇ m.
• PET polyethylene terephthalate
• 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° for 1 minute to form a hydrophilic resin layer with a thickness of 2.4 ⁇ m.
• (Meth)acrylic resin A is a copolymer of styrene, methacrylic acid, and methyl methacrylate (content of each monomer: 52% by mass/29% by mass/19% by mass, Mw: 70,000, Tg 130°C, acid value
• This is a 1:1 mixed solution of propylene glycol monomethyl ether acetate (189 mgKOH/g) and propylene glycol monomethyl ether (solid content concentration: 30.0% by mass).
• a specific composition having the following composition was applied to the surface of the hydrophilic resin layer and dried in an oven at 80° for 1 minute to form a water-soluble intermediate layer with a thickness of 1.0 ⁇ m, thereby obtaining a specific laminate. Note that the coating amount was 27 mL/m 2 .
• a composition for forming a photosensitive resin layer having the following composition was coated on the surface of the water-soluble intermediate layer, and dried in an oven at 80° for 1 minute to form a photosensitive resin layer with a thickness of 2.2 ⁇ m.
• a synthetic resin layer was formed.
• the photosensitive resin layer of the specific laminate was laminated on the copper foil side surface of a polyethylene terephthalate film with copper foil (hereinafter referred to as PET film with copper).
• the lamination conditions were a roll temperature of 100° C. and a lamination speed of 4 m/min.
• the specific film A hydrophobic resin layer
• the specific film B hydrophilic resin layer having recesses formed on the surface of the copper-coated PET film.
• a SEM image of the surface of the specific film A on which the convex structure was formed was obtained using a scanning electron microscope (manufactured by Hitachi High-Tech, S-4800, magnification: 30,000 times).
• Figure 1 shows a SEM image.
• the long axis of the convex structure was measured from the above SEM image, it was confirmed that it was in the range of 0.18 ⁇ m to 0.53 ⁇ m, and that 122 convex structures were formed per 10 ⁇ m 2 of the surface.
• a test piece of the specific film A was prepared using an ultramicrotome, an SEM image of the cross section was obtained using the scanning electron microscope, and the average height of the convex structure was measured to be 62 nm.
• the major axis of the concave structure on the surface of the specific film B on which the concave structure was formed was measured in the same manner as the convex structure, and was found to be in the range of 0.12 ⁇ m to 0.74 ⁇ m. Furthermore, it was confirmed that 72 concave structures were formed per 10 ⁇ m 2 of the surface.
• Figure 2 shows a SEM image. A SEM image of the cross section of specific film B was obtained in the same manner as specific film A, and the average depth of the concave structure was measured, and it was found to be 72 nm.
• 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 ⁇ m.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the convex structures of specific film A was measured and found to be in the range of 0.08 ⁇ m to 0.18 ⁇ m, indicating that 837 convex structures were formed per 10 ⁇ m 2 of the surface. confirmed.
• the average height of the convex structure was measured in the same manner as in Example 1-1, and was found to be 31 nm.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the concave structures of specific film B was measured and found to be in the range of 0.04 ⁇ m to 0.14 ⁇ m, indicating that 826 concave structures were formed per 10 ⁇ m 2 of the surface. confirmed.
• the average depth of the concave structure was measured in the same manner as in Example 1-1 and was found to be 45 nm.
• Example 1-3 A specific laminate was produced in the same manner as in Example 1-2, except that the ratio of water content to methanol content (water content/methanol content) in the specific composition was changed to 3/7. , Specific Film A and Specific Film B were manufactured.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the convex structures of specific film A was measured and found to be in the range of 0.13 ⁇ m to 0.26 ⁇ m, indicating that 566 convex structures were formed per 10 ⁇ m 2 of the surface. confirmed.
• the average height of the convex structure was measured in the same manner as in Example 1-1, and was found to be 54 nm.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the concave structures of specific film B was measured and found to be in the range of 0.06 ⁇ m to 0.19 ⁇ m, indicating that 525 concave structures were formed per 10 ⁇ m 2 of the surface. confirmed.
• the average depth of the concave structure was measured in the same manner as in Example 1-1 and was found to be 56 nm.
• Example 1-4 A specific laminate was produced in the same manner as in Example 1-2, except that the ratio of water content to methanol content (water content/methanol content) in the specific composition was changed to 2/8. , Specific Film A and Specific Film B were manufactured.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the convex structures of specific film A was measured and found to be in the range of 0.08 ⁇ m to 0.24 ⁇ m, indicating that 269 convex structures were formed per 10 ⁇ m 2 of the surface. confirmed.
• Figure 3 shows a SEM image. The average height of the convex structure was measured in the same manner as in Example 1-1, and was found to be 355 nm.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the concave structures of specific film B was measured and found to be in the range of 0.08 ⁇ m to 0.29 ⁇ m, and it was found that 400 concave structures were formed per 10 ⁇ m 2 of the surface. confirmed.
• Figure 4 shows a SEM image. The average depth of the concave structure was measured in the same manner as in Example 1-1 and was found to be 126 nm.
• Example 1-5> A specific laminate, specific film A, and specific film B were prepared 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 ⁇ m. was manufactured.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the convex structures of specific film A was measured and found to be in the range of 0.16 ⁇ m to 0.82 ⁇ m, indicating that 115 convex structures were formed per 10 ⁇ m 2 of the surface. confirmed.
• the average height of the convex structure was measured in the same manner as in Example 1-1, and was found to be 65 nm.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the concave structures of specific film B was measured and found to be in the range of 0.21 ⁇ m to 0.80 ⁇ m, indicating that 49 concave structures were formed per 10 ⁇ m 2 of the surface. confirmed.
• the average depth of the concave structure was measured in the same manner as in Example 1-1 and was found to be 163 nm.
• 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.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the convex structures of specific film A was measured and found to be in the range of 0.49 ⁇ m to 1.27 ⁇ m, indicating that 18 convex structures were formed per 10 ⁇ m 2 of the surface. confirmed.
• the average height of the convex structure was measured in the same manner as in Example 1-1, and was found to be 128 nm.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the concave structures of specific film B was measured and found to be in the range of 0.46 ⁇ m to 1.22 ⁇ m, indicating that 23 concave structures were formed per 10 ⁇ m 2 of the surface. confirmed. The average depth of the concave structure was measured in the same manner as in Example 1-1 and was found to be 189 nm.
• Example 1-7 A specific laminate, specific film A, and specific film B were produced in the same manner as in Example 1-5, except that (meth)acrylic resin A in the hydrophilic resin composition was changed to (meth)acrylic resin B.
• (Meth)acrylic resin B is a propylene glycol monomethyl ether solution of a copolymer of styrene and acrylic acid (content of each monomer: 71% by mass/29% by mass, Mw: 8000, Tg 102°C, acid value 225mgKOH/g). (solid content concentration: 30.0% by mass).
• Example 1-1 In the same manner as in Example 1-1, the long axis of the convex structure of specific film A was measured and found to be in the range of 0.53 ⁇ m to 1.25 ⁇ m, and 1.8 convex structures were formed per 10 ⁇ m 2 of the surface. This was confirmed. The average height of the convex structure was measured in the same manner as in Example 1-1 and was found to be 469 nm.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the concave structures of specific film B was measured and found to be in the range of 0.26 ⁇ m to 1.38 ⁇ m, and 1.9 concave structures were formed per 10 ⁇ m 2 of the surface. This was confirmed. The average depth of the concave structure was measured in the same manner as in Example 1-1 and was found to be 688 nm.
• Example 1-8> A specific laminate, specific film A, and specific film B were produced in the same manner as in Example 1-5, except that (meth)acrylic resin A in the hydrophilic resin composition was changed to (meth)acrylic resin C.
• (Meth)acrylic resin C is a propylene glycol monomethyl ether solution of a copolymer of styrene and acrylic acid (content of each monomer: 71% by mass/29% by mass, Mw: 13000, Tg 102°C, acid value 225mgKOH/g). (solid content concentration: 30.0% by mass).
• Example 1-1 In the same manner as in Example 1-1, the long axis of the convex structures of specific film A was measured to be 0.26 ⁇ m to 0.30 ⁇ m, and it was confirmed that 44 convex structures were formed per 10 ⁇ m 2 of the surface. Ta. The average height of the convex structure was measured in the same manner as in Example 1-1, and was found to be 198 nm.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the concave structures of specific film B was measured to be 0.32 ⁇ m to 0.85 ⁇ m, and it was confirmed that 45 concave structures were formed per 10 ⁇ m 2 of the surface. Ta. The average depth of the concave structure was measured in the same manner as in Example 1-1 and was found to be 251 nm.
• Example 1-9 The thickness of the hydrophilic resin layer was changed to 2.4 ⁇ m, the copper-coated PET film was changed to adhesive tape (manufactured by Nitto Denko Corporation, polyester adhesive tape No. 31B), and a photosensitive resin layer was not formed. Except for this, a specific laminate, specific film A, and specific film B were produced in the same manner as in Example 1-5.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the convex structures of specific film A was measured to be 0.42 ⁇ m to 1.72 ⁇ m, and it was confirmed that 15 convex structures were formed per 10 ⁇ m 2 of the surface. Ta. The average height of the convex structure was measured in the same manner as in Example 1-1 and was found to be 106 nm.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the concave structure of specific film B was measured to be 0.44 ⁇ m to 1.15 ⁇ m, and it was confirmed that 16 concave structures were formed per 10 ⁇ m 2 of the surface. Ta. The average depth of the concave structure was measured in the same manner as in Example 1-1 and was found to be 133 ⁇ m.
• Example 1-10> The specific composition was prepared in the same manner as in Example 1-5, except that the thickness of the hydrophilic resin layer was changed to 2.4 ⁇ m, the specific composition was changed to the following composition, and the photosensitive resin layer was not formed. A laminate, a specific film A, and a specific film B were manufactured. Note that since the specific composition contained only water and methanol, no water-soluble intermediate layer was formed.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the convex structures of specific film A was measured to be 0.37 ⁇ m to 1.12 ⁇ m, and it was confirmed that 28 convex structures were formed per 10 ⁇ m 2 of the surface. Ta. The average height of the convex structure was measured in the same manner as in Example 1-1, and was found to be 168 nm.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the concave structure of specific film B was measured to be 0.14 ⁇ m to 1.12 ⁇ m, and it was confirmed that 26 concave structures were formed per 10 ⁇ m 2 of the surface. Ta. The average depth of the concave structure was measured in the same manner as in Example 1-1 and was found to be 226 nm.
• Example 1-11> A specific laminate, specific film A, and 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
• Example 1-1 In the same manner as in Example 1-1, the long axis of the convex structures of specific film A was measured to be 2.51 ⁇ m to 4.11 ⁇ m, indicating that 1.4 convex structures were formed per 10 ⁇ m 2 of the surface. confirmed.
• the average height of the convex structure was measured in the same manner as in Example 1-1 and was found to be 20 nm.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the concave structures of specific film B was measured to be 2.01 ⁇ m to 4.19 ⁇ m, indicating that 1.9 concave structures were formed per 10 ⁇ m 2 of the surface. confirmed.
• the average depth of the concave structure was measured in the same manner as in Example 1-1 and was found to be 2035 nm.
• Example 1-1 A hydrophobic resin layer with a thickness of 5 ⁇ m was formed on one surface of a PET film in the same manner as in Example 1-1. The surface of the hydrophobic resin layer was observed in the same manner as in Example 1-1, but no convex structure or concave structure was formed.
• Example 1-2 A laminate was produced in the same manner as in Example 1-1 except that the hydrophobic resin layer was not formed.
• the photosensitive resin layer of the above laminate was laminated on the copper foil side surface of the copper-coated PET film.
• the lamination conditions were a roll temperature of 100° C. and a lamination speed of 4 m/min.
• the film (hydrophilic resin layer) formed on the surface of the copper-coated PET film was separated from the support at the interface between the hydrophilic resin layer and the support of the specific laminate. The surface of the film was observed in the same manner as in Example 1-1, but no convex or concave structures were formed.
• Example 1-5 A laminate, film A, and film B were produced in the same manner as in Example 1-5, except that the specific composition was not used. When the surfaces of Film A and Film B were observed in the same manner as in Example 1-1, no convex structure or concave structure was formed.
• Example 2-1 A polyethylene terephthalate (PET) film with a thickness of 25 ⁇ m was prepared as a support.
• the hydrophobic resin composition used in Example 1-1 was melt-extruded on both sides of the support to form a 5 ⁇ m thick hydrophobic resin layer. Thereafter, a 16 um polyethylene terephthalate (PET) film was bonded to both surfaces of the hydrophobic resin layer as a protective film.
• PET polyethylene terephthalate
• Example 1-1 After peeling off the protective film on one side and applying the hydrophilic resin composition used in Example 1-1 to the exposed surface of the hydrophobic resin layer, it was dried in an oven at 80° for 1 minute to a thickness of 1. A 6 ⁇ m hydrophilic resin layer was formed.
• Example 1-4 The specific composition used in Example 1-4 was applied to the surface of the hydrophilic resin layer and dried in an oven at 80° for 1 minute to obtain a specific laminate. Note that the coating amount was 27 mL/m 2 .
• the photosensitive resin layer forming composition 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 determine the thickness. A 2.2 ⁇ m photosensitive resin layer was formed.
• the photosensitive resin layer of the specific laminate was laminated on the copper foil side surface of the copper-coated PET film.
• the lamination conditions were a roll temperature of 100° C. and a lamination speed of 4 m/min.
• Example 1-1 After peeling off the protective film on the other side and applying the hydrophilic resin composition used in Example 1-1 to the exposed surface of the hydrophobic resin layer, it was dried in an oven at 80° for 1 minute to a thickness of 1. A hydrophilic resin layer of .6 ⁇ m was formed.
• Example 1-4 The specific composition used in Example 1-4 was applied to the surface of the hydrophilic resin layer and dried in an oven at 80° for 1 minute to obtain a specific laminate. Note that the coating amount was 27 mL/m 2 .
• the photosensitive resin layer forming composition 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 determine the thickness. A 2.2 ⁇ m photosensitive resin layer was formed.
• the photosensitive resin layer of the obtained specific laminate was laminated on the copper foil side surface of the copper-coated PET film.
• the lamination conditions were a roll temperature of 100° C. and a lamination speed of 4 m/min.
• the specific film A hydrophobic resin layer
• the specific film B hydrophilic resin layer having recesses formed on the surface of the copper-coated PET film.
• a laminate of a support and specific film A formed on both sides of the support is hereinafter referred to as a support-attached film.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the convex structures of specific film A was measured and found to be 0.08 ⁇ m to 0.24 ⁇ m, and it was confirmed that 269 convex structures were formed per 10 ⁇ m 2 of the surface. Ta.
• the average height of the convex structure was measured in the same manner as in Example 1-1 and was found to be 355 ⁇ m.
• the water contact angle of the surface of the specific film A on which the convex structure was formed was measured in the same manner as in Example 1-1, and was found to be 140°.
• Example 1-1 In the same manner as in Example 1-1, the long axis of the concave structures of specific film B was measured to be 0.08 ⁇ m to 0.29 ⁇ m, and it was confirmed that 400 concave structures were formed per 10 ⁇ m 2 of the surface. Ta. The average depth of the concave structure was measured in the same manner as in Example 1-1 and was found to be 126 ⁇ m. The water contact angle of the surface of the specific film B on which the concave structure was formed was measured in the same manner as in Example 1-1, and was found to be 120°.

Landscapes

• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Laminated Bodies (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=88200598

Family Applications (1)

Country Status (4)

Citations (6)

• 2022
  • 2022-10-17 WO PCT/JP2022/038637 patent/WO2023188481A1/ja not_active Ceased
  • 2022-10-17 CN CN202280094207.2A patent/CN118946453A/zh active Pending
  • 2022-10-17 JP JP2024511180A patent/JPWO2023188481A1/ja not_active Abandoned
  • 2022-11-01 TW TW111141479A patent/TW202339972A/zh unknown

Patent Citations (6)

Also Published As

Similar Documents

Legal Events