KR20210007421A - Preparation method of film and film - Google Patents

Abstract

The present application provides a method for producing a film capable of efficiently and efficiently producing a film having excellent physical properties such as transparency or hardness, and having a controlled surface shape suitable for various uses, and a film manufactured by the method. According to the present application, the film can be applied to a variety of uses, including lenses, display substrates, optical waveguides, solar cell substrates, and/or optical disks.

Description

Preparation method of film and film {Preparation method of film and film}

The present application relates to a method of manufacturing a film and a film.

The transparent resin film has excellent optical properties and is hard to break compared to glass, so it can be considered as a material that can replace glass.

As a method of manufacturing a transparent resin film, a method also referred to as a so-called cell casting method, a method of curing after injecting a curable composition into a cell, or by casting a curable composition on a steel belt (flow casting). , A method of curing, and the like are known.

The cell casting method is known in Patent Document 1 or the like, but this method cannot continuously produce a film, and the efficiency is also poor.

A method of casting a curable composition on a steel belt and curing it is known in Patent Document 2 or the like, but in this method, it is difficult to manufacture a film having uniform physical properties.

Patent Document 1: Japanese Patent Laid-Open Publication No. 1996-132455 Patent Document 2: Japanese Patent Laid-Open Publication No. 1992-080007

The object of the present application is to provide a method of manufacturing a film and a film manufactured by the method. This application provides a film manufacturing method that can efficiently and efficiently produce a film that has excellent properties such as transparency and hardness, and has a controlled surface shape suitable for various uses, and a film manufactured by the method To do it for one purpose.

Among the physical properties mentioned in the present specification, the physical properties in which the measurement temperature and/or the measurement pressure affect the result are the results measured at room temperature and/or atmospheric pressure, unless specifically stated otherwise.

The term room temperature is a natural temperature that is warmed or not reduced to a temperature, and means, for example, any temperature within the range of 10°C to 30°C, about 23°C or about 25°C. In addition, the unit of temperature in this specification is Celsius (°C) unless otherwise specified.

The term atmospheric pressure is a natural pressure that is not pressurized or depressurized, and usually means about 1 atmosphere of atmospheric pressure.

In the case of a property in which the measured humidity affects the result in the present specification, the property is a property measured at natural humidity that is not specifically controlled at the room temperature and/or atmospheric pressure.

In the present application, the term alkyl group, alkylene group or alkoxy group is a straight or branched alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified, It may mean an alkylene group or an alkoxy group, or may mean a cyclic alkyl group having 3 to 20 carbon atoms, 3 to 16 carbon atoms, 3 to 12 carbon atoms, 3 to 8 carbon atoms, or 3 to 6 carbon atoms, an alkylene group or an alkoxy group.

In the present application, the term alkenyl group refers to a straight or branched alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms unless otherwise specified, or , It may mean a cyclic alkenyl group having 3 to 20 carbon atoms, 3 to 16 carbon atoms, 3 to 12 carbon atoms, 3 to 8 carbon atoms, or 1 to 6 carbon atoms.

In the present application, the term aryl group or arylene group may mean an aryl group or arylene group having 6 to 24 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms, or a phenyl group or a phenylene group, unless otherwise specified. have.

In the present application, the term epoxy group may mean a cyclic ether having three cyclic atoms or a monovalent residue derived from a compound containing the cyclic ether, unless otherwise specified. Examples of the epoxy group include a glycidyl group, an epoxy alkyl group, a glycidoxyalkyl group, or an alicyclic epoxy group. In the above, the alicyclic epoxy group may mean a monovalent moiety derived from a compound including an aliphatic hydrocarbon ring structure, and a structure in which two carbon atoms forming the aliphatic hydrocarbon ring also form an epoxy group. As the alicyclic epoxy group, an alicyclic epoxy group having 6 to 12 carbons may be exemplified, and for example, a 3,4-epoxycyclohexylethyl group and the like may be exemplified.

The alkyl group, alkylene group, alkoxy group, alkenyl group, aryl group, arylene group, or epoxy group may be optionally substituted with one or more substituents.

The method of manufacturing the film of the present application may include irradiating the energy ray-curable composition layer with an energy ray in a state in which the energy ray-curable composition layer is in contact with the anti-glare film. In the above, the energy ray-curable composition layer is a layer formed by using an energy ray-curable composition, and may mean, for example, a layer formed by coating or casting the layer.

In the present application, the term energy ray-curable composition refers to a composition that is cured by irradiation of energy rays.

In the present application, the term energy rays include microwaves, infrared rays (IR), ultraviolet rays (UV), X-rays and gamma rays, as well as alpha-particle beams, proton beams, and Neutrons. A particle beam such as a neutron beam or an electron beam may be included. Typically, ultraviolet rays or electron beams are used as energy rays.

In the present application, the term anti-glare film refers to a film including a surface formed to exhibit low reflectance for at least a partial region of visible light or the entire visible light region. The surface formed to exhibit the low reflectivity may be referred to as an anti-glare surface.

The anti-glare surface of the anti-glare film may have various shapes, but generally has an uneven surface having a certain level of roughness. The present applicant, by irradiating energy rays to the layer in a state in which the uneven surface of the anti-glare film is in contact with the energy ray-curable composition layer to cure the energy ray-curable composition, thereby having excellent physical properties including hardness characteristics and optical characteristics. It has been discovered that a film can be formed.

In addition, through the above process, the uneven surface of the anti-glare film may be irradiated on the surface of the film, and the uneven surface transferred in this way increases the utilization of the film. For example, the film to which the uneven surface is transferred may exhibit a low reflectance for a part or all of the visible light region by itself, or may be combined with a necessary layer to exhibit the low reflectance. Therefore, such a film can be effectively applied in various applications requiring low reflectivity along with high surface hardness and/or flexibility.

In the present application, the anti-glare surface in contact with the energy ray-curable composition layer may be an uneven surface as described above, and in this case, the arithmetic mean roughness (Ra) of the surface is in the range of about 0.01 μm to 2 μm Can be tomorrow. In such a range, it may be possible to manufacture a film of desired physical properties through the application of an anti-glare surface, which is an uneven surface having an arithmetic average roughness. The arithmetic mean roughness can be measured in the manner disclosed in the examples to be described later. Such arithmetic mean roughness is 0.05 μm or more, 0.1 μm or more, 0.15 μm or more, 0.2 μm or more, or 0.25 μm or more, or 1.8 μm or less, 1.6 μm or less, 1.4 μm or less, 1.2 μm or less, 1 μm or less, 0.9 It may be about μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, or 0.4 μm or less.

In the present application, the anti-glare surface in contact with the energy ray-curable composition layer may be a surface having a 60 degree gloss in the range of 10% to 90%. In such a range, it may be possible to manufacture a film with a desired physical property through the application of the anti-glare surface, which is a surface having a 60 degree gloss. The 60 degree gross can be measured in the manner disclosed in Examples to be described later. Such 60 degree gross is in other instances 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, 85% or less, 80% or less, 75% or less or 70 It may be less than or equal to %.

In the present application, the anti-glare surface in contact with the energy ray-curable composition layer may be a surface exhibiting a haze of 3% to 50%. In such a range, it may be possible to manufacture a film having a desired physical property through the application of an anti-glare surface, which is a surface having a haze. The haze can be measured by the method disclosed in Examples to be described later. In another example, such haze may be 3.5% or more, 4% or more, or 4.5% or more, or 45% or less, 40% or less, 35% or less, 30% or less, or 25% or less.

The type of anti-glare film that can be applied in the present application is not particularly limited, and for example, an anti-glare film having an uneven surface having the aforementioned haze, 60 degree gross and/or arithmetic average roughness Ra can be applied.

In a suitable example, as the anti-glare film, a film having an anti-glare layer including a binder resin and particles may be used.

At this time, as the binder resin, a heat or energy ray-curable binder resin may be applied, and a specific example thereof is not particularly limited, but application of an energy ray-curable binder resin may be advantageous in terms of a process. The type of energy ray-curable binder resin that can be used is not particularly limited, but a non-urethane-based polyfunctional acrylate compound may be applied to secure an appropriate effect. For example, as the compound, a compound having two or more curable functional groups (ex. (meth)acryloyloxy group, etc.) may be applied. The number of functional groups of the compound may be 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or 3 or less. Examples of such compounds include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and neo Neopentylglycol adipate di(meth)acrylate, hydroxyl puivalic acid, neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone modified Dicyclopentenyl di(meth)acrylate, ethylene oxide modified di(meth)acrylate, di(meth)acryloxy ethyl isocyanurate, allylated cyclohexyl di(meth)acrylate, tricyclo Decane dimethanol (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, neopentyl glycol modified 2, such as trimethylpropane di(meth)acrylate, adamantane di(meth)acrylate or 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorine, etc. Functional acrylate; Trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate or propylene oxide Trifunctional acrylates such as modified trimethylolpropane tri(meth)acrylate; Tetrafunctional acrylates such as diglycerin tetra(meth)acrylate or pentaerythritol tetra(meth)acrylate; 5-functional acrylates, such as propionic acid-modified dipentaerythritol penta (meth)acrylate; And a polyfunctional acrylate compound such as a six-functional acrylate such as dipentaerythritol hexa(meth)acrylate or caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like. One or more types may be selected and used in consideration of viscosity and physical properties.

The anti-glare layer may be applied by coating the curable binder resin as described above in a mixed state with particles, and curing by a curing method according to the type of the resin. There is no particular limitation on the type of particles that can be applied, for example, organic polymer particles such as PMMA (poly(methyl methacraylte)) particles or PS (polystyrene) particles, or silica particles or zirconia particles, alumina particles, or titania particles. Inorganic particles and the like can be applied. There is no particular limitation on the shape, average particle diameter and/or ratio of the particles, and particles having an appropriate shape and/or average particle diameter can be applied at an appropriate ratio in consideration of the desired 60 degree gross or haze, arithmetic average roughness Ra, etc. have.

The anti-glare layer may include an optional component additionally required to the component, for example, a silicone-based or fluorine-based slip agent or initiator.

The anti-glare film may include a base film and the anti-glare layer formed on one surface of the base film. In this case, as the base film, an appropriate transmittance, for example, a base film having a transmittance of 80% or more for light having a wavelength of about 370 nm may be used. In other words, since a conventional anti-glare film exists at the outermost part of an optical film, it is provided with a UV blocking function to show low transmittance (50% or less) for a wavelength of 370 nm, but in this application, an anti-glare film It is applied by this mold, and it is necessary to apply a film having high transmittance to ultraviolet rays for the ultraviolet curing process. Therefore, the transmittance as described above can be applied. The type of the base film is not particularly limited as long as it has the transmittance, and for example, a polymer film having the transmittance may be selected from known polymer films.

In the method of the present application, the step of irradiating the energy ray may be performed while the anti-glare surface of the anti-glare film is in contact with the energy ray-curable composition layer.

The energy ray-curable composition layer in contact with the anti-glare film may be formed by casting or coating the energy ray-curable composition. In this case, the method of casting or coating is not particularly limited, and a known method, for example, gravure coating, roll coating, reverse coating, knife coating, die coating, lip coating, doctor coating, extrusion (extrusion) ) Coating, slide coating, wire bar coating, curtain coating, extrusion coating, or spinner coating may be applied. In order to prevent the occurrence of gel-like adhesions or foreign matters during the casting process, the casting is performed under conditions where energy rays are not irradiated, and if necessary, the temperature of the casting may be appropriately controlled.

The thickness of the energy ray-curable composition layer formed by a casting method or the like is not particularly limited, and may be adjusted to an appropriate thickness in consideration of the intended use and casting uniformity. For example, the thickness of the formed layer may be in the range of approximately 1 μm to 1000 μm, but is not limited thereto. In another example, the thickness is 5 μm or more, 10 μm or more, or 15 μm or more, 900 μm or less, 800 μm or less, 700 μm or less, 600 μm or less, 500 μm or less, 400 μm or less, 300 μm or less, 200 μm or less, It may be about 100 μm or less or 50 μm or less.

In the present application, irradiation of energy rays to the energy ray-curable composition may include forming an energy ray-curable composition layer by casting an energy ray-curable composition on a base film; And laminating the anti-glare film on the energy ray-curable composition layer to contact the anti-glare film and the energy ray-curable composition layer. At this time, as described above, the surface of the anti-glare film in contact with the energy ray-curable composition layer may be the aforementioned anti-glare surface.

By applying the above method, it is possible to more stably maintain the uniformity of physical properties and quality of the produced film.

In the above, the type of the base film is not particularly limited, and a base film having an appropriate surface smoothness may be applied. For example, as the base film, polyester film, polypropylene, polyolefin film such as polyethylene or norbornene resin film, acetate film, acrylic film, vinyl fluoride film, polycarbonate film, polyamide film, polya Films such as a related film, cellophane, or polyethersulfone film may be used alone or in combination of two or more. Among these films, an appropriate film may be selected in consideration of required heat resistance and transparency.

As the base film, a transparent film, for example, a film having a light transmittance of 80% or more or 85% or more may be used. The thickness of the base film is not particularly limited, but in consideration of resistance to tension applied in the manufacturing process of the film, warpage or distortion of the laminate, or transmission efficiency of energy rays, the thickness of approximately 10 to 400 μm or 50 to 300 μm It can be selected within a range.

If necessary, a film having a planarization layer formed on one surface thereof may be used as the base film. For example, the energy ray-curable composition layer may be formed on a side without the planarization layer of a base film having a planarization layer formed on one side thereof. Through this method, a film having more excellent surface properties can be manufactured.

There is no particular limitation on the material for forming the planarization layer. In one example, the planarization layer may be formed by coating and curing the energy ray-curable composition applied to the formation of the film on the base film in the same manner.

After casting the energy ray-curable composition on the base film, and laminating the anti-glare surface of the anti-glare film on the cast energy ray-curable composition to prepare a laminate, energy ray irradiation may be performed.

If necessary, the contact between the energy ray-curable composition layer and the anti-glare surface may be pressed with a constant pressure.

In the same manner as described above, the anti-glare film can be prepared by curing the composition by irradiating energy rays in a state in which the anti-glare film is in contact with the energy ray-curable composition layer. At this time, the irradiation direction of the energy ray is not limited, and for example, the energy ray may be irradiated on the anti-glare film side or the side of the energy ray-curable composition layer not in contact with the anti-glare film, or both sides. Even when irradiation of energy rays is performed on the laminate (anti-glare film/energy ray-curable composition layer/base film), energy rays may be irradiated from the anti-glare film side, the base film side, or both sides.

In one example, when the energy ray is irradiated to the laminate, the energy ray may be irradiated to the energy ray-curable composition layer through the base film.

For example, when irradiating ultraviolet rays as energy rays, ultraviolet rays generated using an ultraviolet lamp can be irradiated with ultraviolet rays. As the UV lamp, a metal halide lamp, a high pressure mercury lamp, a low pressure mercury lamp, a pulsed xenon lamp, a xenon/mercury mixture lamp, a low pressure sterilization lamp, and/or an electrodeless lamp may be applied. The irradiation conditions may be determined according to the composition of the energy ray-curable composition, and the like, and may be irradiated so that the exposure amount is approximately 0.01 to 10 mJ/cm ² . The amount of energy to be exposed is about 0.05 mJ/cm ² in another example Above, 0.1 mJ/cm ² Above, 0.5 mJ/cm ² Over, 1 mJ/cm ² Or more than 1.5 mJ/cm ² Or more, or 9 mJ/cm ² Hereinafter, it may be about 8 mJ/cm ² or less, 7 mJ/cm ² or less, 6 mJ/cm ² or less, or 5 mJ/cm ² or less.

내지 35

의 범위 내)에서 수행되지만, 필요하다면, 해당 온도가 조절될 수 있고, 이러한 경우에는, 에너지선의 조사 과정에서 시에는 가열/냉각 장치 등을 적용될 수도 있다.The temperature at which such energy ray irradiation is performed is not particularly limited. Normally, the irradiation of the energy ray is at room temperature (15

To 35

Within the range of), but if necessary, the corresponding temperature can be adjusted, and in this case, a heating/cooling device or the like may be applied during the irradiation of energy rays.

Although there is no particular limitation on the type of the energy ray-curable composition applied in the present application, one having energy ray-curing property and castable flowability or plasticity may be applied in consideration of the casting or coating efficiency. In addition, if necessary, the curing shrinkage rate may be controlled within an appropriate range in order to prevent warping or distortion caused by curing shrinkage before and after curing. Typically, an energy ray-curable composition having a volume shrinkage before and after curing in the range of 3% to 10% may be used.

In addition, a solvent-free composition may be applied in consideration of process efficiency or film properties.

In one example, as the energy ray-curable composition, a composition including at least a silicone resin component and a reactive diluent may be used.

The type of the silicone resin component to be applied is not particularly limited, but in order to more effectively satisfy the desired physical properties, a silicone resin component represented by the following average unit formula 1 may be applied.

[Average Unit Formula 1]

(R ¹ ₃ SiO _1/2 ) _a (R ² ₂ SiO _2/2 ) _b (R ³ SiO _3/2 ) _c (SiO _4/2 ) _d (RO _1/2 ) _e

In the average unit formula 1, R ¹ to R ³ are each independently a hydrogen atom, an alkyl group, an aryl group, or an energy ray-curable group, and when a plurality of R ¹ to R ³ are present, each is the same or different from each other, and R ¹ to At least one of R ³ is an energy ray-curable group, and a, b, c and d are 0≤a≤1, 0<b≤1, 0<c, respectively, when a+b+c+d is converted to 1 ≤1 and 0≤d≤1 are satisfied, and e is a number in which e/(a+b+c+d) falls within the range of 0 to 0.4.

The average unit represents the average ratio of the monomer units contained in the silicone resin component, that is, the so-called M, D, T, and Q units, and that the silicone resin component represents the average unit formula 1, the component When one polymer component (silicone resin) containing a monomer unit is included in a ratio according to the average unit formula 1, or the component contains two or more polymer components (silicone resin), and the two or more components It may mean a case where the average of all included monomer units is defined by the average unit formula 1.

In the average unit formula 1, when a+b+c+d is converted to 1, a and d are each independently 0.95 or less, 0.9 or less, 0.85 or less, 0.8 or less, 0.75 or less, 0.7 or less, 0.65 or less, It may be 0.6 or less, 0.55 or less, 0.5 or less, 0.45 or less, 0.4 or less, 0.35 or less, 0.3 or less, 0.25 or less, 0.2 or less, 0.15 or less, 0.1 or less, or about 0.05 or less.

When a+b+c+d is converted to 1 in the average unit formula 1, b is 0.01 or more, 0.02 or more, 0.03 or more, 0.04 or more, 0.05 or more, 0.06 or more, 0.07 or more, 0.08 or more, 0.09 in other examples. Or more, 0.1 or more, 0.15 or more, 0.2 or more, or 0.25 or more, 0.95 or less, 0.9 or less, 0.85 or less, 0.8 or less, 0.75 or less, 0.7 or less, 0.65 or less, 0.6 or less, 0.55 or less, 0.5 or less, 0.45 or less, 0.4 or less , 0.35 or less, 0.3 or less, or may be about 0.25 or less.

When a+b+c+d is converted to 1 in the average unit formula 1, c is 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, 0.3 or more, 0.35 or more, 0.4 or more, 0.45 or more, 0.5 in other examples. It may be more than, 0.55 or more, 0.6 or more, 0.65 or more, 0.7 or more, or 0.75 or more, or 0.95 or less, 0.9 or less, 0.85 or less, 0.8 or less, or about 0.75 or less.

In the average unit formula ₁ RO _1/2 is, it may indicate a condensing functional groups bonded to the silicon atom. That is, the silicone resin component may be prepared by condensing a condensable silane compound in one example, and the condensation functional group remaining without reaction in the process may be represented by RO _1/2 .

In the average unit formula 1, e may be a number such that e/(a+b+c+d) is in the range of 0 to 0.4. In another example, e/(a+b+c+d) may be about 0.35 or less, about 0.3 or less, about 0.25 or less, about 0.2 or less, about 0.15 or less, about 0.1 or less, or about 0.05 or less.

In the average unit formula 1, R ¹ to R ³ are each a functional group directly bonded to a silicon atom, and a plurality of them may each exist in the silicone resin component represented by the average unit formula 1, and when there are more than one, they may be the same or different. I can. Each of R ¹ to R ³ may independently be a hydrogen atom, an alkyl group, an aryl group, or an energy ray-curable functional group. R ¹ to R ³ is at least one of the energy ray-curable functional group, for example, (at least one of R ³ in the case where R ³ is a plurality), at least it said R ³ may be an energy radiation curable functional group.

In addition, in the average unit formula, R ² may suitably be an alkyl group.

In the above, the type of the energy ray-curable functional group is not particularly limited, and may be, for example, a so-called radical-curable functional group or a cation-curable functional group. Examples of the radical curable functional group include an alkenyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylalkyl group, or a (meth)acryloyloxyalkyl group, and the like. Can illustrate an epoxy group. The term epoxy group, unless otherwise specified, may mean a cyclic ether having three cyclic atoms or a monovalent moiety derived from a compound containing the cyclic ether. Examples of the epoxy group include a glycidyl group, an epoxy alkyl group, a glycidoxyalkyl group, or an alicyclic epoxy group. In the above, the alicyclic epoxy group may mean a monovalent moiety derived from a compound including an aliphatic hydrocarbon ring structure, and a structure in which two carbon atoms forming the aliphatic hydrocarbon ring also form an epoxy group. As the alicyclic epoxy group, an alicyclic epoxy group having 6 to 12 carbon atoms may be exemplified, and for example, a 3,4-epoxycyclohexylethyl group and the like may be exemplified.

Such an energy ray-curable functional group is about 50 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, 70 mol% or more, 75 mol% or more, 80 mol% or more, among all R ¹ to R ³ , It may be present in a ratio of 85 mol% or more, 90 mol% or more, or 95 mol% or more. There is no particular limitation on the upper limit of the ratio of the energy ray-curable functional group, for example, the ratio of the functional group is about 100 mol% or less, about 95 mol% or less, about 90 mol% or less, about 85 mol% or less, about 80 It may be on the order of mole percent or less, about 75 mole percent or less, or about 70 mole percent or less.

The silicone resin component may have a weight average molecular weight (Mw) in the range of 10,000 to 50,000. The weight average molecular weight may be a conversion value of standard polystyrene measured by so-called GPC (Gel Permeation Chromatography). The weight average molecular weight, in another example, about 11000 g/mol or more, 12000 g/mol or more, 13000 g/mol or more, 14000 g/mol or more, 15000 g/mol or more, 16000 g/mol or more, 17000 g/mol Or more, 18000 g/mol or more, 19000 g/mol or more, 20000 g/mol or more, 21000 g/mol or more, 22000 g/mol or more, 23000 g/mol or more, 24000 g/mol or more, 25000 g/mol or more, 26000 g/mol or more, 27000 g/mol or more, 28000 g/mol or more, 29000 g/mol or more, or 30000 g/mol or more, 45000 g/mol or less, 40000 g/mol or less, 35000 g/mol or less, 30000 It may be about g/mol or less, 25000 g/mol or less, or 20000 g/mol or less.

The silicone resin component may also have a molecular weight distribution (PDI, Mw/Mn), that is, a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of about 3 or less. In another example, the molecular weight distribution is 1.1 or more, 1.2 or more, 1.3 or more, 1.4 or more, 1.5 or more, 1.6 or more, 1.7 or more, 1.8 or more, 1.9 or more, 2.0 or more, 2.1 or more, 2.2 or more, 2.8 or less, 2.6 or less, or May be less than 2.4.

The silicone resin component having the above-described average unit and having the above molecular weight characteristic enables effective formation of a film of desired physical properties.

In order to prepare the silicone resin component as described above, a polymerization process for condensing a so-called condensable silane compound (ex. alkoxysilane compound) and a molecular weight control process following the polymerization process are required. Various methods of preparing a silicone resin component by condensing the condensation silane compound in the above are known, and generally, only such a condensation process is performed to prepare a silicone resin component. However, it is difficult to secure molecular weight characteristics of the above-mentioned level simply by polymerization by the condensation process as described above. Therefore, an appropriate molecular weight control process is required following the condensation process.

The molecular weight control process may be performed, for example, while maintaining the polymerization reaction product under reduced pressure conditions at a predetermined temperature. In this process, a solvent, a low molecular weight component, and/or an unreacted product included in the polymerization reaction product are removed, and the molecular weight can be adjusted to a desired level. The decompression condition in the above is not particularly limited, but the decompression process may be performed at a vacuum degree of about 50 to 90 Torr. In another example, the degree of vacuum may be about 55 Torr or more, about 60 Torr or more, or about 65 Torr or more, about 85 Torr or less, about 80 Torr or less, or about 75 Torr or less.

The depressurization process may be performed under a predetermined temperature profile. For example, the depressurization process may include a first step of maintaining the degree of vacuum at the level at a temperature in the range of about 30° C. to 70° C., and then the first step, while maintaining the degree of vacuum at the level, while maintaining the temperature at 60° C. to 100° C. It may include a second step of maintaining within the range of ℃. In the first step, if the above-mentioned degree of vacuum is maintained while maintaining the temperature in the range of about 30° C. to 70° C., the temperature decreases due to reduced pressure, but the temperature drops to a level of about 10° C. to 30° C. Therefore, when the temperature drops as described above, the temperature is raised to the level of the second step again to further perform a molecular weight control process. The temperature of the first step may be about 35°C or more, 40°C or more, or 45°C or more, or 65°C or less, 60°C or less, or 55°C or less in another example, and the temperature of the second step is about 65°C in another example It may be above, 70°C or more, 75°C or more, about 95°C or less, about 90°C or less, or 85°C or less. In addition, in the first step, as mentioned above, a process in which the temperature is substantially lowered to a level of about 10°C to 30°C at a temperature within the range of about 30°C to 70°C may be performed at the aforementioned vacuum degree. have. The time during which the first and second steps are performed is not particularly limited, but in order to secure an appropriate level of molecular weight, the first step is performed for approximately 1 hour to 5 hours, and the second step is approximately 10 minutes to 60 minutes. You can proceed in about a minute.

The method of obtaining the polymerization reactant applied to the above molecular weight control process is not particularly limited. In the industry, various contents of preparing a silicone resin using a condensable compound such as alkoxy silane are known, and all of these methods can be applied in the present application.

In order to advantageously secure the desired molecular weight in the subsequent molecular weight control process, the polymerization process is performed by applying a base catalyst in a mixed solvent of an aqueous solvent and alcohol, ketone and/or acetate in a condensation silane such as alkoxysilane. The method of ordering can be applied.

In the above process, a known compound may be applied as the alkoxy silane.

In addition, as an aqueous solvent that can be applied in the above, for example, water is used, and this aqueous solvent is applied in a ratio of about 0.1 to 10 moles per 1 mole of the total condensable silin compound (ex. alkoxy silane) applied to the polymerization. I can. The ratio of the aqueous solvent may be about 0.5 moles or more, about 1 moles or more, about 1.5 moles or more, about 2 moles or more, or about 2.5 moles or more, about 9 moles or less, about 8 moles or less, about 7 moles or less, It may be about 6 moles or less, about 5 moles or less, about 4 moles or less, or about 3 moles or less.

As the alcohol that can be applied in the above, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, i-butyl alcohol, n-butyl alcohol and/or t-butyl alcohol may be exemplified, and the ketone solvent, Acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl ketone, methyl isopropyl ketone and/or acetyl acetone, etc. may be exemplified, and the acetate solvent includes methyl acetate, ethyl acetate, propyl acetate and/or butyl acetate. It may be illustrated, but is not limited thereto. Such alcohol, ketone, or acetate solvent may be applied in an amount of approximately 0.1 to 10 moles per mole of the total condensable silin compound (ex. alkoxy silane) applied to the polymerization. The proportion of the alcohol, ketone, or acetate solvent may be about 0.5 moles or more, about 1 moles or more, about 1.5 moles or more, about 2 moles or more, or about 2.5 moles or more, about 9 moles or less, about 8 moles or less, about It may be about 7 moles or less, about 6 moles or less, about 5 moles or less, about 4 moles or less, or about 3 moles or less.

In addition, as the base catalyst applied in the above process, for example, an amine compound having a pKa of 15 or less may be applied. In another example, the pKa of the amine compound is about 14.5 or less, about 14 or less, about 13.5 or less, about 13 or less, about 12.5 or less, about 12 or less, about 11.5 or less, about 11 or less, about 10.5 or less, or about 1 or more, It may be about 2 or more, about 3 or more, about 4 or more, about 5 or more, about 6 or more, about 7 or more, about 8 or more, about 9 or more, or about 10 or more, but is not limited thereto. As the amine compound, for example, trialkyl amines such as triethylamine may be applied, but there is no particular limitation as long as pKa is within the above range.

The amine compound may be applied in an amount of about 0.0001 mol to 0.1 mol per 1 mol of the total condensable silin compound (ex. alkoxy silane). In another example, the ratio is about 0.0005 mol or more, about 0.0007 mol or more, about 0.0009 mol or more, or about 0.01 mol or more, or about 0.09 mol or less, about 0.08 mol or less, about 0.07 mol or less, about 0.06 mol or less, about 0.05 mol Hereinafter, it may be about 0.04 mol or less, about 0.03 mol or less, or about 0.02 mol or less.

For example, a polymerization reaction product may be obtained by maintaining the mixture of the above components at a temperature in the range of about 50°C to 110°C for about 8 to 16 hours. The temperature of the polymerization reaction is about 55°C or more, about 60°C or more, about 65°C or more, about 70°C or more, or about 75°C or more, or about 105°C or more, about 100°C or more, about 95°C or more, It may be about 90°C or more or about 85°C or more, and the polymerization time may be about 9 hours or more, about 10 hours or more, or about 11 hours or more, or about 15 hours or less, about 14 hours or less, or about 13 hours or less in another example. May be.

When the polymerized product polymerized in the above manner is introduced into the molecular weight control step, the desired molecular weight characteristics can be more effectively secured.

The energy ray-curable composition may include a reactive diluent together with the component. The reactive diluent may adjust the viscosity of the composition to an appropriate range so that the casting process is properly performed.

As the reactive diluent, known ingredients may be used without particular limitation. A suitable reactive diluent is known depending on the type of curing of the energy ray-curable composition (eg, radical curing type or cationic curing type).

In one example, when the silicone resin component contains a cationic curable functional group (eg, an epoxy group) as an energy ray-curable functional group, an epoxy compound or an oxetane compound may be applied as the reactive diluent.

Epoxy or oxetane compounds that can be applied as reactive diluents in the cationic curable composition are variously known in the art, and such known reactive diluents may be used without limitation.

For example, examples of the epoxy compound or oxetane compound that can be applied as a reactive diluent include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl Ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl Ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)-cyclohexane -1,4-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, vinyl cyclohexene oxide, 4-vinyl epoxycyclohexane, vinylcyclohexene dioxide, limonene oxide, limonene dioxide, bis(3,4- Epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone-modified 3,4 -Epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, β-methyl-δ -Valerolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), bicyclohexyl-3,3'-epoxide , -O-, -S-, -SO-, -SO ₂ -, -C(CH ₃ ) ₂ -, -CBr ₂ -, -C(CBr ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(CCl ₃ ) ₂ -or -CH(C ₆ H ₅ )- bis(3,4-epoxycyclohexyl) having a bond, dicyclopentadiene diepoxide, di(3,4-) of ethylene glycol Epoxy cyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxy hexahydrodioctyl phthalate, epoxy hexahydro-di-2-ethylhexyl phthalate, 1,4-butanediol diglycy Dill Ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, poly Propylene glycol diglycidyl ether, diglycidyl ester of aliphatic long-chain dibasic acid, monoglycidyl ether of aliphatic higher alcohol, phenol, cresol, butyl phenol, or polyether obtained by adding alkylene oxide to these compounds Monoglycidyl ether of teral alcohol, glycidyl ester of higher fatty acids, epoxidized soybean oil, epoxy butyl stearic acid, epoxy octyl stearic acid, epoxidized linseed oil, epoxidized polybutadiene, 1,4-bis[ (3-ethyl-3-oxetanylmethoxy)methyl]benzene, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(3-hydroxypropyl)oxymethyloxetane, 3-ethyl- 3-(4-hydroxybutyl)oxymethyloxetane, 3-ethyl-3-(5-hydroxypentyl)oxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, bis((1-ethyl (3-oxetanyl)methyl)ether, 3-ethyl-3-((2-ethylhexyloxy)methyl)oxetane, 3-ethyl-((triethoxysilylpropoxymethyl)oxetane, 3- (Meth)allyloxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3 -Ethyl-3-oxetanylmethoxy)methyl]benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]-benzene, [1-(3-ethyl-3-oc Cetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol ( 3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether , Dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxygen) Cetanylmethyl) ether or 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, or a combination of two or more selected from the above may be exemplified, but are limited thereto. It is not.

In another example, the silicone resin component is an energy ray-curable functional group as a radical curable functional group (e.g., alkenyl group, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylalkyl group, (meth) In the case of containing an acryloyloxyalkyl group, etc.), various acrylate compounds can be used as the reactive diluent.

As such an acrylate compound, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (Meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate , Isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate or alkyl (meth)acrylate such as tetradecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylic Hydroxyalkyl such as acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate or 8-hydroxyoctyl (meth)acrylate (Meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, Neopentylglycol adipate di(meth)acrylate, hydroxyl puivalic acid neopentylglycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone Modified dicyclopentenyl di(meth)acrylate, ethylene oxide modified di(meth)acrylate, di(meth)acryloxy ethyl isocyanurate, allylated cyclohexyl di(meth)acrylate, tri Cyclodecane dimethanol (meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, ethylene oxide-modified hexahydrophthalic acid di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, neopentyl glycol Such as modified trimethylpropane di(meth)acrylate, adamantane di(meth)acrylate or 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, etc. Bifunctional acrylate; Trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide Trifunctional acrylates such as modified trimethylolpropane tri(meth)acrylate, trifunctional urethane (meth)acrylate, or tris(meth)acryloxyethyl isocyanurate; Tetrafunctional acrylates such as diglycerin tetra(meth)acrylate or pentaerythritol tetra(meth)acrylate; 5-functional acrylates, such as propionic acid-modified dipentaerythritol penta (meth)acrylate; And dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate or urethane (meth)acrylate (ex. of isocyanate monomer and trimethylolpropane tri(meth)acrylate) A polyfunctional acrylate compound such as a 6-functional acrylate such as a reactant may be used, and among them, one or more types may be selected and used in consideration of the desired viscosity and physical properties.

The ratio of the reactive diluent applied in the energy ray-curable composition is adjusted in consideration of the desired viscosity, and there is no particular limitation, but the reactive diluent may be applied in a ratio of 1 to 200 parts by weight relative to 100 parts by weight of the silicone resin component. . In another example, the ratio is 3 parts by weight or more, 5 parts by weight or more, 7 parts by weight or more, or 9 parts by weight or more, or 190 parts by weight or less, 180 parts by weight or less, 170 parts by weight or less, 160 parts by weight or less, 150 parts by weight Or less, 140 parts by weight or less, 130 parts by weight or less, 120 parts by weight or less, 110 parts by weight or less, 100 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, 50 parts by weight It may be about 40 parts by weight or less, 30 parts by weight or less, or about 20 parts by weight or less.

The energy ray-curable composition includes the silicone resin component and the reactive diluent as basic components, and may include necessary additional components. As such an additive component, an initiator capable of initiating curing of the energy ray-curable composition, a dispersant, a surfactant, an antistatic agent, a silane coupling agent, a thickener, a coloring inhibitor, a coloring agent (pigment, dye), an antifoaming agent, a leveling agent, a flame retardant , An ultraviolet absorber, an adhesion imparting agent, a polymerization inhibitor, an antioxidant and/or a surface modifier, and the like may be exemplified, but are not limited thereto.

As an additional component that may be included in the energy ray-curable composition, scattering particles for haze control are also included. These particles usually have a particle diameter capable of scattering light, additionally, particles having a refractive index different from that of the surrounding matrix are applied, and particles having an appropriate level of particle diameter and refractive index may be used in consideration of the desired haze.

By applying the energy ray-curable composition as described above to the above method to prepare a film, a film having desired physical properties can be prepared.

In the manufacturing method of the present application, the above-mentioned energy ray-curable composition layer is cured by irradiating energy rays in the above method, and then the laminate, that is, a laminate or glare of the anti-glare film and the cured energy ray-curable composition layer. The step of cutting and removing the ends of the laminate of the prevention film, the cured energy ray-curable composition layer, and the base film may be additionally performed. Although it can be adjusted according to process variables, etc., undulations may occur at the ends of the film formed in the above manner. When such undulations occur, the desired film can be obtained more effectively by cutting and removing the undulations. This end removal process is optional and may not be performed if there is no need. When the end removal process is performed, there is no particular limitation on the end removal method, for example, the machine saw method, the contour machine method, the shirring method, the lathe method, the gas cutting method, the laser cutting method, and the plasma. A known method such as a cutting method and/or a water jet cutting method may be applied.

Following the above process, if necessary, the process of peeling and removing the base film and/or the anti-glare film applied in the curing process, the process of evaluating the physical properties of the formed film, and/or the process of winding and storing the formed film in a roll shape, etc. This may be done additionally.

This application also relates to a film. In one example, the film may be manufactured by the manufacturing method of the present application.

Accordingly, in one example, the film may be a cured product in the form of a film of an energy ray-curable composition including a silicone resin component having the average unit formula 1 and a reactive diluent. The specific contents of the silicone resin component and the reactive diluent and the ratios therebetween may be the same as those mentioned above.

Since the film is manufactured by the above-described manufacturing method, in one example, the uneven surface of the anti-glare surface of the anti-glare film may have a transferred uneven surface, and the uneven surface may exhibit high surface hardness. have.

For example, the film may be an integrated uneven surface, and the arithmetic mean roughness (Ra) may be in the range of about 0.01 μm to 2 μm. In the above, that the uneven surface is integrated with the film means that the uneven surface is not formed by a separate layer different from the film, and that the corresponding uneven surface is formed on the film itself. I can. The arithmetic mean roughness can be measured in the manner disclosed in the examples to be described later. In other examples, such arithmetic mean roughness is 0.05 μm or more, 0.1 μm or more, 0.15 μm or more, 0.2 μm or more, or 0.25 μm or more, 1.8 μm or less, 1.6 μm or less, 1.4 μm or less, 1.2 μm or less, 1 μm or less, 0.9 It may be about μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, or 0.4 μm or less.

의 온도 및 50%의 상대 습도에서 500 g의 하중 및 45도의 각도로 연필심을 필름의 요철 표면에 긋는 방식으로 측정할 수 있다. 필름의 요철 표면에서 압흔, 긁힘 또는 파열 등과 같은 결함의 발생이 확인될 때까지 연필심의 경도를 단계적으로 증가시키며 연필 경도를 측정할 수 있다. 상기 요철 표면의 연필 경도는 다른 예시에서 대략 6H 이상, 7H 이상, 8H 이상 또는 9H 이상일 수 있다.The uneven surface of the film may also exhibit a pencil hardness of 5H or higher. The pencil hardness, using a general pencil hardness measuring equipment, about 25

It can be measured by drawing the pencil lead on the uneven surface of the film at an angle of 45 degrees and a load of 500 g at a temperature of 50% and a relative humidity of 50%. Pencil hardness can be measured by increasing the hardness of the pencil lead step by step until the occurrence of defects such as indentation, scratch, or rupture on the uneven surface of the film is confirmed. The pencil hardness of the uneven surface may be about 6H or more, 7H or more, 8H or more, or 9H or more in another example.

The uneven surface of the film may exhibit 500 g steel wool resistance of 1,500 or more times. In the above, 500 g steel wool resistance is a surface property found in a steel wool test. 500 g steel wool resistance of the uneven surface of the film is, in other examples, about 2,000 or more, 2,500 or more, 3,000 or more, 3,500 or more, 4,000 or more, 4,500 or more, 5,000 or more , 5,500 or more, 6,000 or more, 6,500 or more, 7,000 or more, 7,500 or more, 8,000 or more, 8,500 or more, 9,000 or more, or 9,500 or more. The steel wool resistance is not particularly limited because it means that the higher the value, the more excellent scratch resistance of the uneven surface of the film is. In one example, the 500 g steel wool resistance may be about 20,000 times or less, about 15,000 times or less, about 10,000 times or less, about 9,000 times or less, or about 8,500 times or less.

The uneven surface of the film may also be a surface having a 60 degree gloss in the range of 30% to 90%. The 60 degree gross can be measured in the manner disclosed in Examples to be described later. Such a 60 degree gross may be 35% or more, 40% or more, 45% or more, 85% or less, 80% or less, 75% or less, or 70% or less in another example.

The uneven surface of the film may also be a surface exhibiting a haze of 3% to 50%. The haze can be measured by the method disclosed in Examples to be described later. In another example, such haze may be 3.5% or more, 4% or more, or 4.5% or more, or 45% or less, 40% or less, 35% or less, 30% or less, or 25% or less.

The film can also have good flexibility. The film of the present application may exhibit, for example, the aforementioned scratch resistance and/or surface hardness, and at the same time exhibit excellent flexibility. For example, the film alone or in combination with another film may exhibit a maximum holding radius of curvature of about 1 to 40 pi. In the above, the maximum holding radius of curvature means the radius of curvature when the film is bent to the maximum without observing defects on the surface of the film when the film is bent according to the Mandrel test according to ASTM D522 standard.

In another example, the radius of curvature is 1.5pi or more, 38 pi or less, 36 pi or less, 34 pi or less, 32 pi or less, 30 pi or less, 28 pi or less, 26 pi or less, 24 pi or less Degree, less than 22 pi, less than 20 pi, less than 18 pi, less than 16 pi, less than 14 pi, less than 12 pi, less than 10 pi, less than 8 pi, less than 6 pi, less than 4 pi It may be about or less than 3 pi.

The film may have a suitable thickness depending on the purpose. Usually, the thickness of the film may be in the range of approximately 1 μm to 1000 μm, but is not limited thereto. In another example, the thickness is 5 μm or more, 10 μm or more, or 15 μm or more, 900 μm or less, 800 μm or less, 700 μm or less, 600 μm or less, 500 μm or less, 400 μm or less, 300 μm or less, 200 μm or less, It may be about 100 μm or less or 50 μm or less.

This application provides a film manufacturing method that can efficiently and efficiently produce a film that has excellent properties such as transparency and hardness, and has a controlled surface shape suitable for various uses, and a film manufactured by the method can do. The film of the present application can be applied to a variety of uses, including lenses, display substrates, optical waveguides, solar cell substrates and/or optical disks.

The scope of the present application will be described in more detail through the following examples, but the scope of the present application is not limited by the following examples.

1. How to measure haze

Haze was measured by using a measuring device (manufacturer: MCRL, product name: HM-150) to allow light to enter the uneven surface of the film, and in a transmission mode method.

2. How to measure 60 degree gloss

60 ° gloss is measured with devices such that light incident on an uneven surface of the film by using the (manufacturer:: BYK, product ^name. BYK Micro Glossmeter60 4561) were measured in reflection mode system.

3. Method of measuring arithmetic mean roughness Ra

The arithmetic average roughness Ra of the uneven surface of the film was confirmed according to ISO 3274 standard.

4. 500 g steel wool resistance evaluation

Steel wool resistance was evaluated using steel wool of grade #0000 sold by Briwax in Europe. Using a measuring equipment (manufacturer: Gibei NT, brand name: KM-M4360), the steel wool was brought into contact with the uneven surface of the film under a load of 500 g, and the steel wool resistance was evaluated while moving left and right. At this time, the contact area was approximately 2 cm and 2 cm in width and length (contact area: 2 cm ² ), respectively. The movement was performed at a speed of about 60 times/min, and the movement distance was about 10 cm. By observing the reflection by visual observation, the steel wool test was performed until indentation, scratch, or rupture was confirmed.

5. Pencil hardness evaluation

의 온도 및 50%의 상대 습도에서 수행하였다.Pencil hardness is measured by using a pencil hardness measuring equipment (manufacturer: Chungbuk Tech, brand name: Pencil Hardness Tester), and drawing the uneven surface of the film with a cylindrical pencil lead at a load of 500 g and an angle of 45 degrees, and indentation, scratches, or rupture, etc. It was measured while increasing the hardness of the pencil lead step by step until the occurrence of the same defect was confirmed. The speed of the pencil lead was about 1 mm/sec, and the moving distance was about 10 mm. These tests are about 25

And 50% relative humidity.

6. Gel Permeation Chromatograph (GPC)

The number average molecular weight (Mn) and molecular weight distribution were measured using GPC (Gel permeation chromatography). In a 5 mL vial, add the material to be analyzed, such as a silicone resin component, and dilute in THF (tetrahydro furan) to a concentration of about 1 mg/mL. Thereafter, the standard sample for calibration and the sample to be analyzed were filtered through a syringe filter (pore size: 0.45 μm) and then measured. Agilent technologies' ChemStation was used as the analysis program, and the weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated by comparing the elution time of the sample with the calibration curve, and the molecular weight distribution (PDI) by the ratio (Mw/Mn). Was calculated. The measurement conditions of GPC are as follows.

<GPC measurement conditions>

Equipment: 1200 series from Agilent technologies

Column: Polymer laboratories' PLgel mixed B 2ea

Solvent: THF

Column temperature: 35℃

Sample concentration: 1mg/mL, 200μL injection

Standard sample: Polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

Preparation Example 1. Preparation of film material

Preparation of silicone resin component

에서 교반하면서 약 12 시간 정도 반응시켜서 1차 반응물을 얻었다. 제조된 1차 반응물의 수평균분자량(Mn)은 약 8341.38 g/mol 정도이고, 분자량 분포(Mw/Mn)는 2.05 정도였다. It was prepared using 3-acryloyloxypropyltrimethoxy (KBM5103, Shinetsu silicon) and dimethyldimethoxysilane (DMDMS, Sigma-Aldrich). The monomer, ethanol, TEA (triethyl amine), and water were uniformly mixed at room temperature in a molar ratio of 0.8:0.2:2.8:2.8:0.01 (KBM5103:DMDMS:ethanol:water:TEA), and 80 in a flask.

It reacted for about 12 hours while stirring at, to obtain a first reaction product. The number average molecular weight (Mn) of the prepared first reactant was about 8341.38 g/mol, and the molecular weight distribution (Mw/Mn) was about 2.05.

The first reactant was maintained at a vacuum condition of 70 Torr and a temperature of 50° C. for about 3 hours. In this process, the temperature dropped to about 20°C due to reduced pressure. Subsequently, while maintaining the vacuum condition again, the temperature was raised to 80° C. and held for 30 minutes to obtain a silicone resin component. The obtained silicone resin component was a component represented by the following average unit formula A, and had a number average molecular weight (Mn) of about 13426.63 g/mol and a molecular weight distribution (Mw/Mn) of about 2.34.

[Average unit formula A]

(Me ₂ SiO _2/2 ) _0.2 (AcSiO _3/2 ) _0.8

In the average unit formula A, Me is a methyl group, and Ac is a 3-acryloyloxypropyl group.

Preparation of solvent-free coating solution

The prepared silicone resin component was mixed with trimethylolpropane triacrylate (TMPTA) in a weight ratio of 9:1 (silicone resin component: TMPTA), and about 2.5 parts by weight of an initiator (Igarcure819) was mixed with respect to 100 parts by weight of the mixture. Thus, a solvent-free coating solution was prepared.

Preparation Example 2. Preparation of anti-glare film for mold (AG1 film)

The anti-glare film for mold is a coating solution on a 100 μm-thick PET (poly(ethylene terephthalate)) base film (TA063, Toyobo), and is a non-urethane-based polyfunctional acrylate, dipentaerythritol hexaacrylate. , Silica particles with an average particle diameter (median particle diameter, D50 particle diameter) of about 1 μm, a fluorine-based slip agent (manufacturer: 3M, product name: FC4430) and a radical initiator (manufacturer: Dupont, product name: Igarcure819) were 100:12:0.1:2 A coating solution prepared by diluting a coating solution containing a weight ratio of (non-urethane-based polyfunctional acrylate: silica particles: slip agent: radical initiator) with a solid content of about 50% by weight in a solvent was coated to a thickness of about 20 μm, After drying at 80° C. for about 2 minutes, it was prepared by irradiating ultraviolet rays with an energy of about 1J/cm ² with an H bulb (Fusion). The arithmetic mean roughness Ra of the anti-glare surface of the prepared anti-glare film was at the level of 0.2 to 0.4 μm, and the 60 degree gross was 45%.

Preparation Example 3. Preparation of anti-glare film for mold (AG2 film)

As a coating solution, dipentaerythritol hexaacrylate, a non-urethane multifunctional acrylate, silica particles having an average particle diameter (median particle diameter, D50 particle diameter) of about 1 μm, a fluorine-based slip agent (manufacturer: 3M, product name: FC4430) and a radical initiator (manufacturer: Dupont, product name: Igarcure819) in a weight ratio of 100:9:0.1:2 (non-urethane multifunctional acrylate: silica particles: slip agent: radical initiator) in a solvent. An anti-glare film was prepared in the same manner as in Preparation Example 2, except that a coating solution prepared by diluting with a solid content of about wt% was used. The arithmetic mean roughness Ra of the anti-glare surface of the film was at the level of 0.2 to 0.4 μm, and the 60 degree gross was 65%.

Example 1.

The solvent-free coating solution of Preparation Example 1 was coated to a thickness of about 20 μm on the side of the PET (poly(ethylene terephthalate)) film on which the planarization layer having a thickness of about 20 μm was formed on one side without the planarization layer. Anti-glare prevention of the anti-glare film (AG2 film) of Preparation Example 3 on the coating layer (coating layer formed on the opposite side of the flattening layer) followed by ultraviolet rays with an energy of 2 J/cm ² using a D bulb (Fusion) Irradiation in the direction of irradiating the coating layer through the anti-glare film with an energy of 2 J/cm ² using a D bulb (Fusion) with the surface in contact so that no air bubbles or air layers are mixed. Then, the PET film side was further irradiated by 2 to prepare a film. The uneven structure was integrally formed on the surface that was in contact with the anti-glare surface of the manufactured film. The haze measured on the uneven surface was about 5.2%, the 60 degree gross was about 65.8%, and the arithmetic mean roughness Ra was about 0.26 μm. In addition, the steel wool resistance of the uneven surface was 10000 times or more, and the pencil hardness was about 9H.

Example 2.

The solvent-free coating solution of Preparation Example 1 was coated to a thickness of about 20 μm on the side of the PET (ethylene terephthalate) (PET) film having the same planarization layer as in Example 1 without the planarization layer. Subsequently, the anti-glare surface of the anti-glare film of Preparation Example 2 was contacted and pressed on the coating liquid in the same manner as in Example 1, and ultraviolet rays were irradiated at 4 J/ by using a D bulb (Fusion) from the PET film side. A film was prepared by irradiation with energy of cm ² . The uneven structure was integrally formed on the surface that was in contact with the anti-glare surface of the manufactured film. The haze measured for the uneven surface was about 21.4%, the 60 degree gross was about 46.2%, and the arithmetic mean roughness Ra was about 0.31 μm. In addition, the steel wool resistance of the uneven surface was 10000 times or more, and the pencil hardness was about 9H.

Example 3.

Unlike Example 1, a PET (ethylene terephthalate) (PET) film without a planarization layer was applied. The solvent-free coating solution of Preparation Example 1 was coated on one side of the PET film to a thickness of about 20 μm. Subsequently, the anti-glare surface of the anti-glare film of Preparation Example 3 was contacted and pressed on the coating liquid in the same manner as in Example 1, and ultraviolet rays were irradiated by using a D bulb (Fusion) on the PET film side. A film was prepared by irradiation with energy of cm ² . The uneven structure was integrally formed on the surface that was in contact with the anti-glare surface of the manufactured film. The haze measured for the uneven surface was about 5.1%, the 60 degree gross was about 66.1%, and the arithmetic mean roughness Ra was about 0.26 μm. In addition, the steel wool resistance of the uneven surface was more than 10000 times, and the pencil hardness was about 8H.

Example 4.

Unlike Example 1, a PET (ethylene terephthalate) (PET) film without a planarization layer was applied. The solvent-free coating solution of Preparation Example 1 was coated on one side of the PET film to a thickness of about 20 μm. Then, the anti-glare surface of the anti-glare film of Preparation Example 2 was contacted and pressed on the coating liquid in the same manner as in Example 1, and ultraviolet rays were applied to 2 J/by using a D bulb (Fusion) from the PET film side. A film was prepared by irradiation with energy of cm ² . The uneven structure was integrally formed on the surface that was in contact with the anti-glare surface of the manufactured film. The haze measured for the uneven surface was about 21.1%, the 60 degree gross was about 47.4%, and the arithmetic mean roughness Ra was about 0.32 μm. In addition, the steel wool resistance of the uneven surface was more than 10000 times, and the pencil hardness was about 7H.

Comparative Example 1.

As a known coating solution for forming an anti-glare layer, a coating solution containing 60% by weight or more of a non-urethane-based polyfunctional acrylate having an average functional group 2 or higher is about 15 μm on a TAC film (50 μm, a TAC film having a UV cut function from Fuji). After coating to a thickness of about 80° C. for 2 minutes and drying, the surface having an uneven structure was formed by irradiating ultraviolet rays with an energy of 1 J/cm ² through a Fusion H bulb. The steel wool resistance of the uneven surface was 500 times or less, and the pencil hardness was about 3H.

Comparative Example 2.

As a known coating solution for forming an anti-glare layer, a coating solution containing 60% by weight or more of a non-urethane-based polyfunctional acrylate having an average functional group bifunctional or higher is slightly completely dried on a TAC film (50 μm, a TAC film having a UV cut function from Fuji) After the coating was applied to a thickness of about 15 μm, maintained for 2 minutes at a temperature of 80° C., and dried, ultraviolet rays were irradiated with energy of 1 J/cm ² through Fusion's H bulb to form a surface having an uneven structure. The steel wool resistance of the uneven surface was 500 times or less, and the pencil hardness was about 3H.

Claims (20)

A method of manufacturing a film comprising the step of irradiating energy rays to the energy ray-curable composition layer in a state in which the energy ray-curable composition layer is in contact with the anti-glare surface of the anti-glare film. The method for producing a film according to claim 1, wherein the anti-glare surface in contact with the energy ray-curable composition layer is an uneven surface having a haze in the range of 3% to 50%. The method for producing a film according to claim 1, wherein the anti-glare surface in contact with the energy ray-curable composition layer is an uneven surface having an arithmetic mean roughness Ra in a range of 0.01 μm to 2 μm. The method for producing a film according to claim 1, wherein the anti-glare surface in contact with the energy ray-curable composition layer is an uneven surface having a 60 degree gloss in the range of 10% to 90%. The method for producing a film according to claim 1, wherein the anti-glare surface in contact with the energy ray-curable composition layer is a resin layer surface containing a binder resin and particles. The method for producing a film according to claim 5, wherein the binder resin is a non-urethane-based polyfunctional acrylate compound. The method for producing a film according to claim 5, wherein the particles are organic polymer particles or inorganic particles. The method of claim 1, further comprising: forming an energy ray-curable composition layer by casting an energy ray-curable composition on the base film; And laminating an anti-glare film on the energy ray-curable composition layer to contact the anti-glare film and the energy ray-curable composition layer. The method of claim 8, wherein a planarization layer is formed on a side opposite to a side on which the energy ray-curable composition of the base film is cast. The method of claim 1, wherein the energy ray-curable composition comprises a silicone resin component having the following average unit formula 1 and a reactive diluent:
[Average Unit Formula 1]
(R ¹ ₃ SiO _1/2 ) _a (R ² ₂ SiO _2/2 ) _b (R ³ SiO _3/2 ) _c (SiO _4/2 ) _d (RO _1/2 ) _e
In the average unit formula 1, R ¹ to R ³ are each independently a hydrogen atom, an alkyl group, an aryl group, or an energy ray-curable group, and when a plurality of R ¹ to R ³ are present, each is the same or different from each other, and R ¹ to At least one of R ³ is an energy ray-curable group, and a, b, c and d are 0≤a≤1, 0<b≤1, 0<c, respectively, when a+b+c+d is converted to 1 ≤1 and 0≤d≤1 are satisfied, and e is a number in which e/(a+b+c+d) falls within the range of 0 to 0.4. The method for producing a film according to claim 10, wherein the weight average molecular weight of the silicone resin component is in the range of 10,000 to 50,000, and the molecular weight distribution is 2.3 or less. The method for producing a film according to claim 10, wherein the reactive diluent is an epoxy compound, an oxetane compound, or an acrylate compound. The method of claim 10, wherein the energy ray-curable composition comprises 1 to 200 parts by weight of a reactive diluent based on 100 parts by weight of the silicone resin component. The method for producing a film according to claim 10, wherein the energy ray-curable composition further comprises an initiator. It is a cured product of an energy ray-curable composition comprising a silicone resin component and a reactive diluent having the following average unit formula 1,
A film in which at least one surface is formed of an integrated uneven surface with a pencil hardness of 5H or more:
[Average Unit Formula 1]
(R ¹ ₃ SiO _1/2 ) _a (R ² ₂ SiO _2/2 ) _b (R ³ SiO _3/2 ) _c (SiO _4/2 ) _d (RO _1/2 ) _e
In the average unit formula 1, R ¹ to R ³ are each independently a hydrogen atom, an alkyl group, an aryl group, or an energy ray-curable group, and when a plurality of R ¹ to R ³ are present, each is the same or different from each other, and R ¹ to At least one of R ³ is an energy ray-curable group, and a, b, c and d are 0≤a≤1, 0<b≤1, 0<c, respectively, when a+b+c+d is converted to 1 ≤1 and 0≤d≤1 are satisfied, and e is a number in which e/(a+b+c+d) falls within the range of 0 to 0.4. The film according to claim 15, wherein the uneven surface exhibits 500 g steel wool resistance of 1,500 or more times. The film according to claim 15, wherein the weight average molecular weight of the silicone resin component is in the range of 10,000 to 50,000, and the molecular weight distribution is 2.3 or less. The film according to claim 15, wherein the haze on the uneven surface is in the range of 3% to 50%. The film according to claim 15, wherein the arithmetic mean roughness Ra of the uneven surface is in the range of 0.01 μm to 2 μm. The film according to claim 15, wherein the uneven surface has a 60 degree gloss in the range of 10% to 90%.