JP6505993B2 - PHOTO-CURABLE COMPOSITION, AND LAMINATED FILM - Google Patents

Description

  The present invention relates to a photocurable composition particularly suitable for a protective coating layer laminated on at least one side of a base film made of a cyclic olefin resin, and a laminated film.

  In recent years, as a base film material of an electrode film for a touch panel, a cyclic olefin-based resin film excellent in high transparency, low hygroscopicity, and refractive index stability is used (see, for example, Patent Document 1). The cyclic olefin-based resin film is preferable in terms of characteristics such as transparency and hygroscopicity, but the flexibility is not sufficient. In addition, since the surface hardness is relatively low, the scratch resistance is low and the surface is easily scratched. For this reason, providing a hard-coat layer in cyclic olefin resin film is performed.

  However, in a conventional laminated film in which a hard coat layer is provided on a cyclic olefin resin film, cracks may occur not only on the hard coat layer but also on the surface of the cyclic olefin resin film in a flexibility test.

JP, 2012-66477, A

  The present invention has been proposed in view of such conventional circumstances, and provides a photocurable composition and a laminate film from which excellent flexibility can be obtained.

  As a result of intensive investigations, the inventor of the present invention has obtained a laminated film having excellent flexibility by using a polyether urethane (meth) acrylate oligomer and setting the breaking elongation to a predetermined value or more when photopolymerized. I found that I could get it.

That is, the photocurable composition according to the present invention comprises a trifunctional or higher functional (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, a polyether urethane (meth) acrylate oligomer, a photopolymerization initiator And the content of the trifunctional or higher functional (meth) acrylate monomer is 5 to 50% by mass, and the content of the bifunctional (meth) acrylate monomer is 5 to 50% by mass, The content of the polyether-based urethane (meth) acrylate oligomer is 40 to 80% by mass, and the breaking elongation at a thickness of 80 μm when photopolymerized is 35% or more.

In addition, the laminated film according to the present invention includes a base film made of a cyclic olefin-based resin, and a protective coat layer formed on at least one side of the base film, and the protective coat layer is trifunctional or higher A content of the trifunctional or higher functional (meth) acrylate monomer containing a meta) acrylate monomer, a bifunctional (meth) acrylate monomer, a polyether urethane (meth) acrylate oligomer, and a photopolymerization initiator And 5 to 50% by mass, the content of the bifunctional (meth) acrylate monomer is 5 to 50% by mass, and the content of the polyether-based urethane (meth) acrylate oligomer is 40 to 80%. % a and elongation at break in the thickness 80μm upon photopolymerization, it by photopolymerization of the photocurable composition is 35% or more The thickness of the protective coating layer, characterized in that a 1 to 4 [mu] m.

In addition, the method for producing a laminated film according to the present invention comprises: a trifunctional or higher functional (meth) acrylate monomer; a bifunctional (meth) acrylate monomer; a polyether urethane (meth) acrylate oligomer; And the content of the trifunctional or higher functional (meth) acrylate monomer is 5 to 50% by mass, and the content of the bifunctional (meth) acrylate monomer is 5 to 50% by mass, A photocurable composition having a polyether urethane (meth) acrylate oligomer content of 40 to 80% by mass and having a breaking elongation at a thickness of 80 μm of 35% or more when photopolymerized is Applying at least one surface of a substrate film made of a resin, and photopolymerizing the photocurable composition to obtain at least one of the substrate film Thickness on one side and having a forming step for forming a protective coating layer is 1μm or more 4μm or less.

  According to the present invention, a laminated film having excellent flexibility can be obtained by using a polyether urethane (meth) acrylate oligomer and setting the elongation at break when photopolymerized to a predetermined value or more.

FIG. 1 is a cross-sectional view showing an example of a laminated film. FIG. 2 is a cross-sectional view showing an example of a laminated film for a touch panel. FIG. 3 is a cross-sectional view showing an example of a laminated film for a touch panel.

Hereinafter, embodiments of the present invention will be described in detail in the following order with reference to the drawings.
1. Photocurable composition 2. Laminated film 3. Method of manufacturing laminated film 4. First embodiment 5. Second embodiment

<1. Photocurable composition>
The photocurable composition according to the present embodiment comprises a trifunctional or higher functional (meth) acrylate monomer (component (A)), a bifunctional (meth) acrylate monomer (component (B)), and a polyether urethane. A (meth) acrylate oligomer (component (C)) and a photopolymerization initiator (component (D)) are contained, and the breaking elongation at a thickness of 80 μm when photopolymerized is 35% or more. In the present specification, (meth) acrylate is a meaning that includes acrylic acid ester (acrylate) and methacrylic acid ester (methacrylate).

[Component (A): (meth) acrylate monomer having three or more functional groups]
The component (A) is for improving the adhesion to the cyclic olefin resin and the reactivity of the photocurable composition itself. Such component (A) is a polymerizable compound having three or more acrylate residues or methacrylate residues (hereinafter, (meth) acrylate residues) in the molecule, and is used in the field of adhesives and the like It can be used by appropriately selecting from trifunctional or higher (meth) acrylate monomers.

  Specific examples of the component (A) include pentaerythryl triacrylate (PETA), 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO conversion triacrylate, ε-caprolactone modified tris-(-2acryloxy) Ethyl) isocyanurate, trimethylolpropane triacrylate (TMPTA), ε-caprolactone modified tris (acroxyethyl) acrylate, ethoxylated (20) trimethylolpropane triacrylate, propoxylated (3) trimethylolpropane triacrylate, propoxylated (6) trimethylolpropane triacrylate, ethoxylated (9) trimethylolpropane triacrylate, propoxylated (3) glyceryl triacrylate, ethoxylated (4) pentacene The lysitol tetraacrylate, the pentaerythritol tetraacrylate, the ditrimethylol propane tetraacrylate, the dipentaerythritol pentaacrylate, the dipentaerythritol hexaacrylate (DPHA) etc. are mentioned, These 1 type (s) or 2 or more types can be used. Among these, pentaerythritol triacrylate can be preferably used in terms of adhesion, reactivity, crosslinkability, surface hardness and the like. As a specific example that can be obtained on the market, trade name “M305” of Toagosei Co., Ltd., trade name “TMM-3L” of Shin-Nakamura Chemical Co., Ltd., and the like can be mentioned.

  If the content of the component (A) in the photocurable composition is too small, properties such as adhesion, reactivity, crosslinkability and surface hardness tend to deteriorate, and if too large, properties such as flexibility and curling Since it tends to deteriorate, it is preferably 5 to 50% by mass, more preferably 15 to 40% by mass.

[Component (B): bifunctional (meth) acrylate monomer]
The component (B) is for improving the adhesion to the cyclic olefin resin and the reactivity of the photocurable composition itself, as with the trifunctional or higher (meth) acrylate monomer. Such component (B) is a polymerizable compound having two acrylate residues or methacrylate residues (hereinafter, (meth) acrylate residues) in the molecule, and is used in the field of adhesives and the like 2 It can be used by appropriately selecting from functional (meth) acrylate monomers.

  Specific examples of the component (B) include dimethylol-tricyclodecane diacrylate, bisphenol AEO modified diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, propoxylated bisphenol A diacrylate, and trilyl. Cyclodecane dimethanol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, polyethylene glycol (200) diacrylate, tetraethylene glycol diacrylate, polyethylene glycol (400) diacrylate, cyclohexane di Methanol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated cyclohexane dimethanol diacrylate Ethoxylated (4) bisphenol A diacrylate, ethoxylated (10) bisphenol A diacrylate, polyethylene glycol (600) diacrylate, alkoxylated neopentyl glycol diacrylate, dioxane glycol diacrylate, isocyanuric acid EO converted diacrylate etc. And one or more of these can be used. Among these, dimethylol-licyclodecane diacrylate can be preferably used in terms of adhesion, reactivity, crosslinkability, surface hardness and the like. As a specific example which can be obtained on the market, trade name "DCP-A" of Kyoeisha Chemical Co., Ltd. can be mentioned.

  If the content of the component (B) in the photocurable composition is too small, properties such as adhesion, reactivity, crosslinkability and surface hardness tend to deteriorate, and if too large, properties such as flexibility and curling Since it tends to deteriorate, it is preferably 5 to 50% by mass, more preferably 5 to 15% by mass.

[Component (C): polyether-based urethane (meth) acrylate oligomer]
Component (C) is a compound having a unit derived from a polyether polyol compound in the molecule, a polymerizable (meth) acryloyl group, and a urethane bond. Component (C) is, for example, a terminal isocyanate urethane prepolymer obtained by reacting polyether polyol compound (X) and polyvalent isocyanate compound (Y) with (meth) acrylate (Z) having a hydroxy group. It is obtained by

  The polyether polyol compound (X) can be obtained, for example, by addition polymerization of an alkylene oxide using a polyhydric alcohol as an initiator. Specific examples of the polyether polyol compound (X) include, for example, polyhydric alcohols such as polytetramethylene glycol ("PTMG"), polypropylene glycol ("PPG"), polyethylene glycol ("PEG"), and ethylene oxide, Copolymers with alkylene oxides such as propylene oxide can be mentioned.

  Examples of the polyvalent isocyanate compound (Y) include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate ( Modified MDI), hydrogenated xylylene diisocyanate (H-XDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMXDI), tetramethyl xylylene diisocyanate (m-TMXDI), isophorone Diisocyanate (IPDI), norbornene diisocyanate (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane ( 6XDI), and the like.

  As (meth) acrylate (Z) having a hydroxy group, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) Acryloyl phosphate, 4-butylhydroxy (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) ) Acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified 2-hydroxyethyl (meth) Acrylate, and the like.

  Specific examples of the component (C) which can be obtained on the market include “UT5490”, “UT5467”, “UT5489”, “UT5522”, “UT5523”, “UT5495”, trade names of Nippon Synthetic Chemical Industry Co., Ltd. UT 5496 "," UT 5497 "," UT 5506 "and the like can be mentioned.

Moreover, it is preferable that the oligomer elongation (breaking elongation) of a component (C) is 5 to 300%. Moreover, it is preferable that the at least 1 sort (s) of oligomer elongation of component (C) is 200% or more. Oligomer elongation after drying with a bar coater a composition prepared by blending 100 parts by mass of component (C) and 3 parts by mass of 2-hydroxy-2-cyclohexylacetophenone as a photopolymerization initiator into a PET film subjected to peeling treatment After coating to a thickness of 80 μm, photopolymerization is carried out under an irradiation condition of 300 mJ / cm ² , and this cured film (specimen: 70 mm × 20 mm) is subjected to a tensile tester (product name: Tensilon) by a method according to JIS K7127. Using ORIENTEC Co., Ltd., it can be drawn at a speed of 0.5 mm / min, and can be expressed as an elongation (%) when the test piece is cut (broken). In addition, when the solvent is contained in the oligomer, it measures after volatilizing a solvent before and behind photocuring as needed.

  If the content of the component (C) in the photocurable composition is too small, the flexibility tends to be deteriorated, and if too large, the scratch resistance tends to be deteriorated, so preferably 40 to 80% by mass More preferably, it is 55-70 mass%.

[Component (D): Photopolymerization initiator]
As a component (D), it can select suitably from known radical photopolymerization initiators, and can use it. As a component (D), an acetophenone type photoinitiator, a benzyl ketal type photoinitiator, a phosphorus type photoinitiator etc. are mentioned, for example, 1 type (s) or 2 or more types of these can be used.

  Specific examples of the component (D) which can be obtained on the market include 2-hydroxy-2-cyclohexylacetophenone (IRGACURE 184, manufactured by BASF Japan Ltd.), α-hydroxy-α, as an acetophenone photopolymerization initiator. α'-Dimethylacetophenone (DAROCUR 1173, manufactured by BASF Japan Ltd.), 2,2-dimethoxy-2-phenylacetophenone (IRGACURE 651, manufactured by BASF Japan Ltd.), 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone (DAROCUR 2959, manufactured by BASF Japan Ltd.), 2-hydroxy-1- {4- [2-hydroxy-2-methyl-propionyl] -benzyl} phenyl} -2 -Methyl-pro Down-1-one (IRGACURE (IRGACURE) 127, manufactured by BASF Japan Ltd.) and the like. Also, as a benzil ketal photopolymerization initiator, benzophenone, fluorenone, dibenzosuberone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 4-hydroxybenzophenone, 4-chlorobenzophenone, 4,4'-dichlorobenzophenone, etc. Can be mentioned. Bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide (IRGACURE 819, manufactured by BASF Japan Ltd.), (2,4,6-trimethyl benzoyl-diphenyl phosphine) as a phosphorus-based photopolymerization initiator Oxide (DAROCURE TPO, manufactured by BASF Japan Ltd.) etc. are mentioned, Among these, it is preferable to use an acetophenone photopolymerization initiator from the viewpoint of realizing smooth photocuring.

  If the content of the component (D) in the photocurable composition is too small, the adhesive performance tends to decrease due to a reduction in hardness performance and the hardness is insufficient, and if too large, properties such as adhesion due to polymerization failure are The content is preferably 0.5 to 25% by mass, and more preferably 1 to 10% by mass, because it tends to decrease.

[Other ingredients]
Moreover, it is preferable that a photocurable composition contains an inorganic fine particle (component (E)) as needed in addition to component (A)-component (D) mentioned above. Thereby, the refractive index can be adjusted and the surface can be roughened, and the antiblocking performance can be improved.

  As component (E), metal oxide fine particles such as silicon oxide (silica), aluminum oxide, zirconium oxide and the like can be mentioned. In addition, it is preferable that the surface treatment is performed by a coupling agent or the like, and in particular, in order to enhance the affinity and binding with the binder component, the surface treatment with a silane coupling agent having an alkyl group or a (meth) acryloyl group. Preferably it is done.

  Specific examples of component (E) which can be obtained on the market include CIK Nanotech Co., Ltd. trade name: M23, H83, E83, M06, M44, H94, M18, E65, H58, K26, Nissan Chemical Industries, Ltd. Trade names: methanol silica sol, MEK-ST (silica sol dispersed in methyl ethyl ketone), IPA-ST (silica sol dispersed in isopropyl alcohol), and the like.

  The component (E) is preferably an aggregate having an average particle diameter of 10 nm or more and 50 nm or less. By using the aggregates, it is possible to prevent the particle size of the micro order and to suppress the rise of the haze. In the case of an aggregate of primary particles, the average particle diameter of the component (E) is an image obtained by visual observation or image photograph from the image photograph of secondary electron emission obtained by scanning electron microscope (SEM) etc. It can be determined by processing or measuring with a particle size distribution analyzer using dynamic light scattering method, static light scattering method or the like. Here, the average particle size refers to the number average particle size. Also, when the particles are not spherical, they mean the diameter of a circle corresponding to the projected area.

  If the content of the component (E) in the photocurable composition is too small, the anti-blocking performance tends to decrease, and if too large, the haze tends to increase, so it is preferably 7 to 15% by mass, more preferably Preferably it is 9-13 mass%.

  In addition, the photocurable composition contains additives such as a solvent, a leveling agent, a hue control agent, a coloring agent, an ultraviolet absorber, an antistatic agent, various thermoplastic resin materials and the like within the range not impairing the effects of the present invention. can do. As the antistatic agent, for example, conductive carbon, inorganic fine particles, inorganic fine powder, surfactant, ionic liquid and the like can be used. These antistatic agents may be used alone or in combination of two or more. As a material of an inorganic fine particle and an inorganic fine powder, the material which has an electroconductive metal oxide as a main component is mentioned, for example. As the conductive metal oxide, for example, tin oxide, indium oxide, ATO (antimony-doped tin oxide), ITO (indium-doped tin oxide), antimony zinc oxide or the like can be used.

  In addition, the photocurable composition is produced by uniformly mixing the components (A) to (D) described above, and if necessary, the component (E) and various additives according to a conventional method.

The photocurable composition described above has a breaking elongation at a thickness of 80 μm of 35% or more when photopolymerized. Further, the breaking elongation is preferably 60% or less. Thereby, excellent flexibility and scratch resistance can be obtained. The Martens hardness at a thickness of 80 μm when photopolymerized is preferably 100 N / mm ² or more. The higher the Martens hardness, the better the scratch resistance can be obtained.

  Such a photocurable composition is particularly useful as a composition of a protective coating layer formed on at least one side of a substrate film comprising a cyclic olefin resin. Thereby, in a flexibility test, it can control that a crack arises in the surface of a protection coat layer and a cyclic olefin system resin film. Moreover, since it is excellent also in abrasion resistance, it can utilize preferably for a touch-panel use.

<2. Laminated film>
The laminated film according to the present embodiment includes a base film made of a cyclic olefin-based resin, and a protective coat layer formed on at least one side of the base film, and the protective coat layer is trifunctional or higher (meth) Acrylate monomer (component (A)), bifunctional (meth) acrylate monomer (component (B)), polyether urethane (meth) acrylate oligomer (component (C)), photopolymerization initiator (component (component (C)) D) and photopolymerizing a photocurable composition having a breaking elongation at a thickness of 80 μm of 35% or more.

  FIG. 1 is a cross-sectional view showing an example of a laminated film. The laminated film 13 has a structure in which the protective coating layer 12 is laminated on both sides of the base film 11.

  The base film 11 is formed by forming a cyclic olefin resin in a sheet form. As cyclic olefin resins, resins (COP) having an alicyclic structure in the main chain having cycloolefin as a monomer obtained by ring-opening metathesis polymerization of cyclic olefins (for example, norbornenes) and subsequent hydrogenation reaction, The resin (COC) obtained by the addition polymerization of cyclic olefin (for example, norbornenes) and alpha-olefin (for example, ethylene) is mentioned.

  Specific examples of COP include polytetracyclododecene specified by Nippon Zeon Co., Ltd. under the trade name "ZEONOR". Further, as a specific example of COC, an ethylene norbornene copolymer specified by TOPAS Advanced Polymers under the trade name "TOPAS", and ethylene tetracyclododecene identified by Mitsui Chemicals, Inc. under the trade name "APEL"・ Methacrylic acid ester copolymer etc. can be mentioned. A phase difference function may be imparted to the film made of these cyclic olefin resins by a known method.

  The thickness of the substrate film 11 is usually 25 to 200 μm, preferably 40 to 150 μm, although it varies depending on the type and performance of the optical device to which it is applied. The breaking elongation at a thickness of 80 μm of the base film 11 is usually 20% or less regardless of the MD direction and the TD direction, that is, regardless of the in-plane direction of the film.

  The protective coating layer 12 is formed by photopolymerizing the above-described photocurable composition. The thickness of the protective coating layer 12 is usually 0.5 to 8 μm, preferably 0.8 to 7 μm. The protective coating layer 12 may be laminated on only one side of the base film 11.

  According to such a laminated film, it is possible to suppress the occurrence of cracks on the surface of the base film 11 and the protective coating layer 12 in the flexibility test. Moreover, since it is excellent also in abrasion resistance, it can utilize preferably for a touch-panel use.

  FIG.2 and FIG.3 is sectional drawing which shows an example of the laminated | multilayer film for touchscreens. In the laminated film 15A for a touch panel shown in FIG. 2, the protective coating layer 12 is formed on both sides of the base film 11, and further, a known transparent electrode 14 such as ITO is formed on the surface of the protective coating layer 12. In addition, in the laminated film 15B for a touch panel shown in FIG. 3, an optical adjustment layer 16 such as a well-known retardation film or the like is formed between the protective coating layer 12 and the transparent electrode 14.

  Thus, it can be preferably used as a lamination film for a touch panel by forming a transparent electrode using an ITO film, conductive fine particles, a nanowire-shaped material or the like on at least one surface of the lamination film by a known method. Furthermore, by laminating such a laminate film for a touch panel on an image display element such as a liquid crystal display element or an organic EL display element, it can be preferably applied as an image display / input device of a smart phone or a personal computer.

<3. Method of manufacturing laminated film>
The method for producing a laminated film according to the present embodiment includes a trifunctional or higher functional (meth) acrylate monomer (component (A)), a bifunctional (meth) acrylate monomer (component (B)), and a polyether urethane. (C) a photocurable composition containing a (meth) acrylate oligomer (component (C)) and a photopolymerization initiator (component (D)) and having a breaking elongation of 35% or more at a thickness of 80 μm when photopolymerized And coating the photocurable composition on at least one side of the base film made of cyclic olefin resin, and forming the protective coating layer on at least one side of the base film by photopolymerizing the photocurable composition. .

  Hereinafter, an adjustment step of adjusting the photocurable composition, a pretreatment step of pretreating the base film, an application step of applying the photocurable composition, and a forming step of forming the protective coating layer will be described. .

[Adjustment process]
First, in addition to the components (A) to (D) described above, a photocurable composition containing inorganic fine particles (component (E)), if necessary, may be further added according to a conventional method Mix evenly and adjust. It is preferable that the photocurable composition not only has translucency but also that the hue of transmitted light and the amount of transmitted light do not change significantly due to coloring and haze.

  The solvent is not particularly limited as long as it can sufficiently dissolve, for example, a resin raw material to be used, and a known organic solvent can be used. Examples of the organic solvent include ketone solvents such as MEK, MIBK and ANON; alcohol solvents such as IPA, n-BuOH and t-BuOH; ester solvents such as butyl acetate and ethyl acetate; glycol ether solvents and the like It can be mentioned.

[Pretreatment process]
Next, in order to improve the adhesion between the substrate film and the cured product layer made of the photocurable composition, one surface or both surfaces of the substrate film are subjected to a surface treatment by an oxidation method or an unevenness forming method. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet process), flame treatment, hot air treatment, ozone / ultraviolet radiation treatment and the like.

[Coating process]
Next, the photocurable composition prepared as described above is applied onto a substrate film. The coating method is not particularly limited, and known methods can be used. Examples of known coating methods include microgravure coating, wire bar coating, direct gravure coating, die coating, dipping, spray coating, reverse roll coating, curtain coating, comma coating, knife coating And spin coating.

[Formation process]
Next, the photocurable composition coated on the base film is dried and cured to form a protective coat layer made of the photocurable composition. Thereby, a film with a protective coat layer is obtained.

  The drying conditions are not particularly limited, and may be natural drying or artificial drying in which the drying humidity, drying time, and the like are adjusted. However, when wind is applied to the surface of the paint during drying, it is preferable that wind marks do not occur on the surface of the coating. This is because when the wind pattern occurs, the coating appearance is deteriorated and the thickness unevenness of the surface property occurs.

  As the light for curing the photocurable composition, energy rays such as gamma rays, alpha rays and electron rays can be applied in addition to ultraviolet rays.

<4. First embodiment>
In the first embodiment, a trifunctional or higher functional (meth) acrylate monomer (component (A)), a bifunctional (meth) acrylate monomer (component (B)), and a urethane (meth) acrylate oligomer (component (C) ) And a photopolymerization initiator (component (D)) were prepared. And the breaking elongation and the Martens hardness of the cured film which photopolymerized the photocurable composition were measured. Moreover, the cured layer which consists of a photocurable composition was formed on both surfaces of a base film, the laminated film was produced, and the high-speed flexibility of the laminated film and abrasion resistance were evaluated. The present invention is not limited to these examples.

  Measurement of elongation at break, measurement of Martens hardness, preparation of laminated film, evaluation of high-speed flexibility of laminated film, and evaluation of scratch resistance of laminated film were performed as follows.

[Measurement of elongation at break]
The photocurable composition was applied to the release-treated PET film with a bar coater, and then the photocurable composition was photopolymerized under an irradiation condition of 300 mJ / cm ² to obtain a cured film having a thickness of 80 μm. A cured film (test piece: 70 mm × 20 mm) is pulled at a speed of 0.5 mm / min using a tensile tester (product name: Tensilon, Inc.) by a method according to JIS K 7127, and the test piece is cut The elongation at break was determined. For practical use, the breaking elongation of the cured film is desirably 35% or more.

Moreover, it measured similarly about the breaking elongation of each component of component (A)-component (C). A composition obtained by blending 100 parts by mass of a component to be measured and 3 parts by mass of 2-hydroxy-2-cyclohexylacetophenone as a photopolymerization initiator into a PET film subjected to peeling treatment so that the thickness after drying with a bar coater becomes 80 μm The coated film was photopolymerized under irradiation conditions of 300 mJ / cm ² , and this cured film (specimen: 70 mm × 20 mm) was subjected to tensile testing by the method according to JIS K 7127 (product name: TENSILON, ORIENTEC Co., Ltd.) ) At a speed of 0.5 mm / min to determine the elongation (%) when the test piece is broken (broken). In addition, when the solvent contained in the oligomer, it measured, after volatilizing a solvent before and behind photocuring as needed.

[Measurement of Martens hardness]
The photocurable composition was applied to the release-treated PET film with a bar coater, and then the photocurable composition was photopolymerized under an irradiation condition of 300 mJ / cm ² to obtain a cured film having a thickness of 80 μm. The opposite side of the measurement surface of the cured film (test piece: 70 mm × 20 mm) was fixed to a slide glass with Aon Alpha manufactured by Toagosei Co., Ltd. The surface hardness was measured with a Vickers indenter such that an arbitrary position on the measurement surface was selected and the maximum indentation depth was 10% or less of the average thickness of the cured film. The measurement was performed using a Martens hardness tester (HM500, Fisher Instruments Co., Ltd.). Practically, the Martens hardness of the cured film is desired to be 100 N / mm ² or more. In order to minimize the influence of the adhesive for fixing, it is preferable to apply the adhesive as thin as possible.

[Production of laminated film]
As a base film, a cyclic olefin resin film having a thickness of 75 μm subjected to corona treatment (a film made by dispersing about 10% of a styrene-based elastomer in a resin component in a COC resin (Less than 6% in both direction and TD direction). The photocurable composition was coated on both sides of this substrate film and then photopolymerized under irradiation conditions of 300 mJ / cm ² to form protective coat layers on both sides of the substrate film, respectively, to obtain a laminated film.

[Evaluation of high-speed flexibility of laminated film]
Perform bending operation to bend the laminated film (test piece: 100m x 20mm) once in the direction of MD (Machine Direction) of the base film, at 10 points at a speed of 60 times per minute, with or without cracks Was observed with a 10 × optical microscope. And the bending location where a crack is not observed at all was counted as good. Depending on the application, it is desirable that the good number of times of high-speed flexibility of the laminated film is ten.

[Evaluation of scratch resistance of laminated film]
Attach a laminated film (specimen: 100 mm x 50 mm) to a scratch tester (product name: Gakushin-type friction fastness tester, Tester Sangyo Co., Ltd.), apply a load of 250 g to # 0000 steel wool, and harden the surface Was carried out 20 times (10 reciprocations), and the presence or absence of a scratch was visually observed. The case where a flaw was not observed at all was evaluated as good "(circle)", and the case where a flaw was observed was evaluated as defect (x).

  In addition, attach a laminated film (specimen: 100 mm x 50 mm) to a scratch tester (product name: Gakushin-type friction fastness tester, Tester Sangyo Co., Ltd.), apply a load of 250 g to an alcohol swab, and make the hardened layer surface The scratch test was performed 20 times (10 reciprocations), and the presence or absence of a scratch was visually observed. The case where a flaw was not observed at all was evaluated as good "(circle)", and the case where a flaw was observed was evaluated as defect (x).

<4-1. Regarding the relationship between breaking elongation and high-speed flexibility>
Example 1
As a trifunctional or higher (meth) acrylate monomer (component (A)), pentaerithryl triacrylate (M-305, manufactured by Toagosei Co., Ltd.), a bifunctional (meth) acrylate monomer (component (B)) As tricyclodecane dimethanol diacrylate (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.), as urethane (meth) acrylate oligomer (component (C1)), polyether-based urethane having a functional group number of 10 and oligomer elongation 9% Oligomer (UT5467, manufactured by Japan Synthetic Chemical Industry Co., Ltd.), a urethane (meth) acrylate oligomer (component (C2)), polyether group urethane oligomer with 2 functional groups and an elongation of 250% of an oligomer (UT5490, Japan Synthetic Chemical As a photopolymerization initiator (component (D)), 2-hydroxy-1- {4- 2-hydroxy-2-methyl - propionyl] - benzyl} phenyl} -2-methyl - using propan-1-one (IRGACURE (IRGACURE) 127, manufactured by BASF Japan Ltd.).

As shown in Table 1, 24.3 wt% of component (A), 9.7 wt% of component (B), 19.4 wt% of component (C1) (UT5467), 43.7 wt% of component (C2) (UT5490), and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

Example 2
As shown in Table 1, the same components as in Example 1 are used, 24.3 wt% of component (A), 9.7 wt% of component (B), 25.0 wt% of component (C1) (UT5467), component (C2) A photocurable composition was prepared by uniformly mixing a solute component concentration of 38.0 wt% of (UT5490) and 3.0 wt% of the component (D) to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

[Example 3]
As shown in Table 1, the same components as in Example 1 are used, 24.3 wt% of component (A), 9.7 wt% of component (B), 13.0 wt% of component (C1) (UT5467), component (C2) A photocurable composition was prepared by uniformly mixing a solute component concentration of 50.0 wt% of (UT5490) and 3.0 wt% of the component (D) to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

Example 4
As shown in Table 1, the same components as in Example 1 are used, 20.8 wt% of component (A), 8.3 wt% of component (B), 20.9 wt% of component (C1) (UT5467), component (C2) A photocurable composition was prepared by uniformly mixing a solute component concentration of 47.0 wt% of (UT5490) and 3.0 wt% of component (D) to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The breaking elongation of the cured film was 49%, and the Martens hardness of the cured film was 118 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

[Example 5]
As shown in Table 1, using the same components as in Example 1, 27.7 wt% of component (A), 11.1 wt% of component (B), 17.9 wt% of component (C1) (UT5467), component (C2) The photocurable composition was prepared by uniformly mixing a solute component concentration of 40.3 wt% of (UT5490) and 3.0 wt% of the component (D) to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 39%, and the Martens hardness of the cured film was 119 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

[Example 6]
As shown in Table 1, using the same components as Example 1, 24.3 wt% of component (A), 9.7 wt% of component (B), 8.0 wt% of component (C1) (UT5467), component (C2) A photocurable composition was prepared by uniformly mixing a solute component concentration of 55.0 wt% of (UT5490) and 3.0 wt% of component (D) to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 61%, and the Martens hardness of the cured film was 94 N / mm ² . The good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was x, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was x.

[Example 7]
As shown in Table 1, the same components as in Example 1 are used, 17.3 wt% of component (A), 6.9 wt% of component (B), 22.4 wt% of component (C1) (UT5467), component (C2) A photocurable composition was prepared by uniformly mixing a solute component concentration of 50.4 wt% of (UT5490) and 3.0 wt% of component (D) to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 56%, and the Martens hardness of the cured film was 95 N / mm ² . The good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was x, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was x.

Comparative Example 1
As shown in Table 1, the same components as in Example 1 are used, 24.3 wt% of component (A), 9.7 wt% of component (B), 29.1 wt% of component (C1) (UT5467), component (C2) A photocurable composition was prepared by uniformly mixing a solute component concentration of 33.9 wt% of (UT5490) and 3.0 wt% of component (D) to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 31%, and the Martens hardness of the cured film was 140 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 8, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

Comparative Example 2
As shown in Table 1, the same components as in Example 1 were used, 31.2 wt% of component (A), 12.5 wt% of component (B), 16.4 wt% of component (C1) (UT5467), component (C2) A photocurable composition was prepared by uniformly mixing a solute component concentration of 36.9 wt% of (UT5490) and 3.0 wt% of component (D) to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 34%, and the Martens hardness of the cured film was 134 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 7, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

As in Comparative Examples 1 and 2, when the breaking elongation of the cured film is less than 35%, the evaluation results of high-speed flexibility deteriorate. On the other hand, when the breaking elongation of a cured film is 35% or more like Examples 1-7, the evaluation result of a favorable high-speed flexibility was obtained. Moreover, it turned out that favorable mar resistance (steel wool, alcohol cotton swab) is obtained when Martens hardness is 100 N / mm < ² > or more like Examples 1-5.

<4-2. About the relationship between component (D) and high-speed flexibility>
Next, the relationship between the component (D) and high-speed flexibility was examined. As component (D1), 2-hydroxy-1- {4- [2-hydroxy-2-methyl-propionyl] -benzyl} phenyl} -2-methyl-propan-1-one (IRGACURE 127, BASF Japan And 2-hydroxy-2-cyclohexylacetophenone (IRGACURE 184, manufactured by BASF Japan Ltd.) as component (D2). The same components as in Example 1 were used except for these.

[Example 8]
As shown in Table 2, 24.5 wt% of component (A), 9.8 wt% of component (B), 19.6 wt% of component (C1) (UT5467), 44.1 wt% of component (C2) (UT5490), and The photocurable composition was prepared by uniformly mixing a solute component concentration of 2.0 wt% of the component (D1), and a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . The good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was x, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was o.

[Example 9]
As shown in Table 2, 24.0 wt% of component (A), 9.6 wt% of component (B), 19.2 wt% of component (C1) (UT5467), 43.2 wt% of component (C2) (UT5490), and The photocurable composition was prepared by uniformly mixing a solute component concentration of 4.0% by weight of the component (D1) to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

[Example 10]
As shown in Table 2, 23.8 wt% of component (A), 9.5 wt% of component (B), 19.0 wt% of component (C1) (UT5467), 42.8 wt% of component (C2) (UT5490), and The photocurable composition was prepared by uniformly mixing a solute component concentration of 5.0% by weight of the component (D1) to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

[Example 11]
As shown in Table 2, 24.3 wt% of component (A), 9.7 wt% of component (B), 19.4 wt% of component (C1) (UT5467), 43.6 wt% of component (C2) (UT5490), and The photocurable composition was prepared by uniformly mixing a solute component concentration of 3.0 wt% of the component (D2) to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . The good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was x, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was o.

  As in Examples 1 to 10, in the range of 2.0 wt% to 5.0 wt% of the component (D1), a good evaluation result of high-speed flexibility was obtained. Moreover, also in the case of the component (D2) as in Example 11, the evaluation result of good high-speed flexibility was obtained. That is, it was found that by using an acetophenone photopolymerization initiator, a good evaluation result of high-speed flexibility can be obtained.

<4-3. About the relationship between the components (A) to (C) and high-speed flexibility>
Next, when the component (A) or the component (B) was not mix | blended, it verified about the high-speed flexibility when a polyether type urethane oligomer is not mix | blended as a component (C). As component (B1), tricyclodecane dimethanol diacrylate (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.), as component (B2), isocyanuric acid EO conversion diacrylate (M 215, manufactured by Toagosei Co., Ltd.), component As (CO1), a caprolactone-based urethane oligomer (UT5236) having a functional group number of 9 and an oligomer elongation of 35%, a urethane acrylate oligomer having a functional group number of 6 and an oligomer elongation of 0.8% as a component (CO2) 2-hydroxy-1- {4- [2-hydroxy-2-methyl-propionyl] -benzyl} phenyl} -2-methyl-propan-1-one (IRGACURE (as a component (D1) IRGACURE) 127, manufactured by BASF Japan Ltd., and 2-hydrocarbon as the component (D2) Shi-2-cyclohexyl-acetophenone was used (IRGACURE (IRGACURE) 184, manufactured by BASF Japan Ltd.). The same components as in Example 1 were used except for these.

Comparative Example 3
As shown in Table 3, without blending the component (B), 34.0 wt% of the component (A), 19.4 wt% of the component (C1) (UT5467), 43.6 wt% of the component (C2) (UT5490), And, a photocurable composition was prepared by uniformly mixing a solute component concentration of 3.0 wt% of the component (D2) to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . The good number of times of high-speed flexibility of the laminated film was 6, the evaluation of the abrasion resistance of the laminated film by the steel wool was x, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was o.

Comparative Example 4
As shown in Table 3, without blending the component (A), 34.0 wt% of the component (B1), 19.4 wt% of the component (C1) (UT5467), 43.6 wt% of the component (C2) (UT5490), And, a photocurable composition was prepared by uniformly mixing a solute component concentration of 3.0 wt% of the component (D2) to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 35%, and the Martens hardness of the cured film was 118 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 5, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

Comparative Example 5
As shown in Table 3, the concentration of the solute component is uniform at 9.7 wt% of component (A), 29.1 wt% of component (B2), 58.2 wt% of component (CO1), and 3.0 wt% of component (D1) The photocurable composition was prepared by mixing to make a 80 μm thick cured film. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 20%, and the Martens hardness of the cured film was 160 N / mm ² . Further, the good number of times of high-speed bending of the laminated film was 4, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

Comparative Example 6
As shown in Table 3, the concentration of the solute component is uniform at 9.7 wt% of component (A), 38.8 wt% of component (B2), 48.5 wt% of component (CO1), and 3.0 wt% of component (D1) The photocurable composition was prepared by mixing to make a 80 μm thick cured film. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The breaking elongation of the cured film was 15%, and the Martens hardness of the cured film was 180 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 2, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

Comparative Example 7
As shown in Table 3, the concentration of the solute component is uniform at 9.7 wt% of component (A), 48.5 wt% of component (B2), 38.8 wt% of component (CO1), and 3.0 wt% of component (D1) The photocurable composition was prepared by mixing to make a 80 μm thick cured film. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 13%, and the Martens hardness of the cured film was 194 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 1, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

Comparative Example 8
As shown in Table 3, 9.7 wt% of component (A), 29.1 wt% of component (B2), 19.4 wt% of component (CO1), 38.8 wt% of component (CO2), and component (D1) 3 A photocurable composition was prepared by uniformly mixing a solute component concentration of 0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 5%, and the Martens hardness of the cured film was 206 N / mm ² . The good number of times of high-speed flexibility of the laminated film was 0, the evaluation of the abrasion resistance of the laminated film by the steel wool was ウ ー ル, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

Comparative Example 9
As shown in Table 3, 9.7 wt% of component (A), 29.1 wt% of component (B2), 29.1 wt% of component (CO1), 29.1 wt% of component (CO2), and component (D1) 3 A photocurable composition was prepared by uniformly mixing a solute component concentration of 0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 7%, and the Martens hardness of the cured film was 194 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 1, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

Comparative Example 10
As shown in Table 3, 9.7 wt% of component (A), 29.1 wt% of component (B2), 38.8 wt% of component (CO1), 19.4 wt% of component (CO2), and component (D1) 3 A photocurable composition was prepared by uniformly mixing a solute component concentration of 0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 10%, and the Martens hardness of the cured film was 182 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 2, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

  As in Comparative Examples 3 and 4, when either the component (A) or the component (B) is not added, good high-speed flexibility evaluation is performed even when the breaking elongation of the cured film is 35% or more. No results were obtained. Further, as in Comparative Examples 5 to 10, when the caprolactone urethane oligomer or the urethane acrylate oligomer is used as the component (C) without blending the polyether urethane oligomer, the breaking elongation of the cured film is 20. It was as low as less than%. Along with that, the evaluation result of high speed flexibility became bad.

<4-4. Regarding the relationship between the type of component (C) and the elongation at break>
Next, the type of component (C) was changed, and the relationship between the type of component (C) and the elongation at break was verified. Component (C1) is a polyether urethane oligomer having 10 functional groups and an oligomer elongation of 9% (UT5467, manufactured by Japan Synthetic Chemical Industry Co., Ltd.), and a component (C2) having a functional group number of 2, an oligomer elongation of 250% Ether-based urethane oligomer (UT5490, manufactured by Japan Synthetic Chemical Industry Co., Ltd.), Component (C3), polyether-based urethane oligomer having 6 functional groups and 34% elongation of oligomer (UT5489, manufactured by Japan Synthetic Chemical Co., Ltd.), component (C4) is a polyether urethane oligomer having 5 functional groups and an oligomer elongation of 72% (UT5522, manufactured by Nippon Gohsei Chemical Co., Ltd.), a polyether having a functional group of 4 and an oligomer elongation of 110% as a component (C5) Urethane oligomer (UT5523, manufactured by Japan Synthetic Chemical Co., Ltd.), having 10 functional groups as component (C6) Polyether-based urethane oligomer with 16% elongation (UT5495, manufactured by Nippon Gohsei Kagaku Co., Ltd.), Component (C7), polyether-based urethane oligomer with 10 functional groups and 13% elongation, oligomer (UT5496, Japan Synthetic Chemical As a component (C8), a polyether urethane oligomer having 10 functional groups and an oligomer elongation of 50% (UT5497, manufactured by Nippon Gohsei Kagaku Co., Ltd.) and a functional group having 10 functional groups as a component (C9) The polyether urethane oligomer (UT5506, Nippon Synthetic Chemical Industry Co., Ltd. product) whose oligomer elongation is 39% was used. The same components as in Example 1 were used except for these.

Comparative Example 11
As shown in Table 4, 24.3 wt% of component (A), 9.7 wt% of component (B), 19.4 wt% of component (C1) (UT5467), 43.6 wt% of component (C3) (UT5489), and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 11%, and the Martens hardness of the cured film was 214 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 2, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

Comparative Example 12
As shown in Table 4, 24.3 wt% of component (A), 9.7 wt% of component (B), 19.4 wt% of component (C1) (UT5467), 43.6 wt% of component (C4) (UT5522), and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 14%, and the Martens hardness of the cured film was 199 N / mm ² . The good number of times of high-speed flexibility of the laminated film was 4, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ×.

Comparative Example 13
As shown in Table 4, 24.3 wt% of component (A), 9.7 wt% of component (B), 19.4 wt% of component (C1) (UT5467), 43.6 wt% of component (C5) (UT5523), and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 18%, and the Martens hardness of the cured film was 183 N / mm ² . The good number of times of high-speed flexibility of the laminated film was 5, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ×.

Comparative Example 14
As shown in Table 4, 24.3 wt% of component (A), 9.7 wt% of component (B), 19.4 wt% of component (C1) (UT5467), 43.6 wt% of component (C6) (UT5495), and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 10%, and the Martens hardness of the cured film was 222 N / mm ² . The good number of times of high-speed flexibility of the laminated film was 0, the evaluation of the abrasion resistance of the laminated film by the steel wool was ウ ー ル, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

Comparative Example 15
As shown in Table 4, 24.3 wt% of component (A), 9.7 wt% of component (B), 19.4 wt% of component (C1) (UT5467), 43.6 wt% of component (C7) (UT5496), and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 10%, and the Martens hardness of the cured film was 223 N / mm ² . The good number of times of high-speed flexibility of the laminated film was 0, the evaluation of the abrasion resistance of the laminated film by the steel wool was ウ ー ル, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

Comparative Example 16
As shown in Table 4, 24.3 wt% of component (A), 9.7 wt% of component (B), 19.4 wt% of component (C1) (UT5467), 43.6 wt% of component (C8) (UT5497), and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 12%, and the Martens hardness of the cured film was 208 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 1, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was x.

Comparative Example 17
As shown in Table 4, 24.3 wt% of component (A), 9.7 wt% of component (B), 19.4 wt% of component (C1) (UT5467), 43.6 wt% of component (C9) (UT5506), and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 11%, and the Martens hardness of the cured film was 212 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 2, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

Comparative Example 18
As shown in Table 4, the solute component of 24.3 wt% of component (A), 9.7 wt% of component (B), 63.0 wt% of component (C4) (UT5522), and 3.0 wt% of component (D) The photocurable composition was prepared by uniformly mixing the concentration to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The breaking elongation of the cured film was 17%, and the Martens hardness of the cured film was 187 N / mm ² . The good number of times of high-speed flexibility of the laminated film was 4, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ×.

Comparative Example 19
As shown in Table 4, the solute component of 24.3 wt% of component (A), 9.7 wt% of component (B), 63.0 wt% of component (C5) (UT5523), and 3.0 wt% of component (D) The photocurable composition was prepared by uniformly mixing the concentration to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 24%, and the Martens hardness of the cured film was 164 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 7, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ×.

[Example 12]
As shown in Table 4, a solute component of 24.3 wt% of component (A), 9.7 wt% of component (B), 63.0 wt% of component (C2) (UT5490), and 3.0 wt% of component (D) The photocurable composition was prepared by uniformly mixing the concentration to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 86%, and the Martens hardness of the cured film was 82 N / mm ² . The good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ×.

Comparative Example 20
As shown in Table 4, the solute component of 24.3 wt% of component (A), 9.7 wt% of component (B), 63.0 wt% of component (C8) (UT5523), and 3.0 wt% of component (D) The photocurable composition was prepared by uniformly mixing the concentration to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 14%, and the Martens hardness of the cured film was 200 N / mm ² . The good number of times of high-speed flexibility of the laminated film was 6, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ×.

  As in Comparative Examples 11 to 20, when a polyether urethane oligomer having an oligomer elongation of less than 200% is used as the component (C), the breaking elongation of the cured film is low. On the other hand, when a polyether urethane oligomer having an oligomer elongation of 200% or more was used as in Examples 1 and 12, the breaking elongation of the cured film was as high as 35% or more. Along with that, the evaluation result of high speed flexibility became bad.

<4-5. Regarding the relationship between the film thickness of the protective coating layer and the high-speed flexibility>
Next, it verified about the relationship between the film thickness of a protective coating layer, and high-speed flexibility. The same components as in Example 1 were used as components (A) to (D).

[Example 13]
As shown in Table 5, a photocurable composition having the same solute component concentration as in Example 1 was prepared, and a cured film having a thickness of 80 μm was produced. Moreover, the 1-micrometer-thick protective coating layer was formed in both surfaces of a 75-micrometer-thick base film, respectively, and the laminated film was produced. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

Example 14
As shown in Table 5, a photocurable composition having the same solute component concentration as in Example 1 was prepared, and a cured film having a thickness of 80 μm was produced. Moreover, the protective coating layer with a thickness of 3 micrometers was formed in both surfaces of a 75-micrometer-thick base film, respectively, and the laminated film was produced. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

[Example 15]
As shown in Table 5, a photocurable composition having the same solute component concentration as in Example 1 was prepared, and a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 4 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

Comparative Example 21
As shown in Table 5, a photocurable composition having the same solute component concentration as in Example 1 was prepared, and a cured film having a thickness of 80 μm was produced. Moreover, the protective coating layer with a thickness of 5 micrometers was formed in both surfaces of a 75-micrometer-thick base film, respectively, and the laminated film was produced. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 8, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○.

  From Example 1 and Examples 13 to 15 and Comparative Example 21, it was found that good high-speed flexibility and scratch resistance can be obtained when the thickness of the protective coating layer is 1 μm or more and 4 μm or less.

<5. Second embodiment>
In the second example, as in the first example, a photocurable composition containing inorganic fine particles (component (E)) in addition to the components (A) to (D) was prepared. Then, the breaking elongation and the Martens hardness of the cured film obtained by photopolymerizing the photocurable composition were measured in the same manner as in the first example. Moreover, the cured layer which consists of a photocurable composition was formed on both surfaces of a base film, the laminated film was produced, and the high-speed flexibility of the laminated film and abrasion resistance were evaluated. Further, the adhesion and the antiblocking function of the laminated film were evaluated, and the surface roughness and the haze of the laminated film were measured. The present invention is not limited to these examples.

  Evaluation of adhesion, evaluation of antiblocking function, measurement of surface roughness, and measurement of haze were performed as follows.

[Evaluation of adhesion]
Straight cuts were made with a cutter to the protective coating layer of the laminated film (50 mm × 50 mm) to form 100 grids. A pressure-sensitive adhesive tape (cellophane tape, Nichiban Co., Ltd.) was attached to the grid, and when peeled off, the number of grids remaining on the laminated film side was counted without being transferred to the adhesive tape. The case where the number was 100 was evaluated as good "○", the case where it was less than 100 and 30 or more was normally evaluated as "△", and the case where it was less than 30 was evaluated as "bad".

[Evaluation of anti blocking function]
The blocking performance value of the laminated film was measured. That is, a laminated film in which the surfaces of the protective coating layer were adhered to each other was cut into strips, a load (g) was applied to an adhesion area of 4 cm ² (2 cm × 2 cm), and the appearance was regarded as a blocking performance value. The case where Newton ring generation state which is an adhesion mark between films is 20 kg or more is evaluated as very good "◎", and the case where it is 10 kg or more and less than 20 kg is evaluated as good "○" and is 300 g or more and less than 10 kg. The case was normally evaluated as "Δ", and the case of less than 300 g was evaluated as defective "×".

[Measurement of surface roughness]
The surface roughness of the protective coating layer of the laminated film was measured using AFM (SPA 400, manufactured by Hitachi High-Tech Science, Inc.).

[Measurement of haze]
The haze of the laminated film was measured according to JIS K 7136 using a haze meter (HM150, manufactured by Murakami Color Research Laboratory).

<5-1. Add component (E) to Example 1>
As a trifunctional or higher (meth) acrylate monomer (component (A)), pentaerithryl triacrylate (M-305, manufactured by Toagosei Co., Ltd.), a bifunctional (meth) acrylate monomer (component (B)) As tricyclodecane dimethanol diacrylate (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.), as urethane (meth) acrylate oligomer (component (C1)), polyether-based urethane having a functional group number of 10 and oligomer elongation 9% Oligomer (UT5467, manufactured by Japan Synthetic Chemical Industry Co., Ltd.), a urethane (meth) acrylate oligomer (component (C2)), polyether group urethane oligomer with 2 functional groups and an elongation of 250% of an oligomer (UT5490, manufactured by Japan Synthetic Chemical (strain) As a photopolymerization initiator (component (D)), 2-hydroxy-1- {4- 2-hydroxy-2-methyl-propionyl] -benzyl} phenyl} -2-methyl-propan-1-one (IRGACURE 127, manufactured by BASF Japan Ltd.), having an alkyl group as (component (E)) An aggregate (M44, manufactured by CIK Nanotech Co., Ltd.) having an average particle diameter of 30 nm surface-treated with a silane coupling agent was used.

Example 1
As shown in Table 6, 24.3 wt% of component (A), 9.7 wt% of component (B), 19.4 wt% of component (C1) (UT5467), 43.7 wt% of component (C2) (UT5490), and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was は, the antiblocking function was x, the surface roughness was 0.5 nm, and the haze was 0.23%.

[Example 16]
As shown in Table 6, the component (E) is added to the component of Example 1, 22.6 wt% of the component (A), 9.0 wt% of the component (B), 18.0 wt% of the component (C1) A photocurable composition is prepared by uniformly mixing the solute component concentration of 40.6 wt% of component (C2) (UT5490), 2.8 wt% of component (D), and 7.0 wt% of component (E) Then, a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), the anti blocking function was x, surface roughness was 2.0 nm, and haze was 0.23%.

[Example 17]
As shown in Table 6, component (E) is added to the component of Example 1, 22.1 wt% of component (A), 8.8 wt% of component (B), 17.7 wt% of component (C1) (UT5467) A photocurable composition is prepared by uniformly mixing the solute component concentration of 39.6 wt% of component (C2) (UT5490), 2.7 wt% of component (D), and 9.0 wt% of component (E) Then, a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ○, the surface roughness was 3.3 nm, and the haze was 0.23%.

[Example 18]
As shown in Table 6, component (E) is added to the component of Example 1, 21.6 wt% of component (A), 8.6 wt% of component (B), 17.3 wt% of component (C1) (UT5467) A photocurable composition is prepared by uniformly mixing the solute component concentration of 38.8 wt% of the component (C2) (UT5490), 2.7 wt% of the component (D), and 11.0 wt% of the component (E) Then, a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ○, the surface roughness was 4.6 nm, and the haze was 0.24%.

[Example 19]
As shown in Table 6, component (E) is added to the component of Example 1, 21.1 wt% of component (A), 8.4 wt% of component (B), 16.9 wt% of component (C1) (UT5467) A photocurable composition is prepared by uniformly mixing the solute component concentration of 38.0 wt% of the component (C2) (UT5490), 2.6 wt% of the component (D) and 13.0 wt% of the component (E) Then, a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 6.0 nm, and the haze was 0.25%.

[Example 20]
As shown in Table 6, component (E) is added to the component of Example 1, 20.6 wt% of component (A), 8.2 wt% of component (B), 16.5 wt% of component (C1) (UT5467) A photocurable composition is prepared by uniformly mixing the solute component concentration of 37.1 wt% of the component (C2) (UT5490), 2.6 wt% of the component (D), and 15.0 wt% of the component (E) Then, a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 41%, and the Martens hardness of the cured film was 125 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 8.0 nm, and the haze was 0.36%.

[Example 21]
As shown in Table 6, a photocurable composition was prepared by uniformly mixing the same solute component concentration as in Example 19, to prepare a cured film having a thickness of 80 μm. Moreover, the 1-micrometer-thick protective coating layer was formed in both surfaces of a 75-micrometer-thick base film, respectively, and the laminated film was produced. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 6.5 nm, and the haze was 0.25%.

Example 22
As shown in Table 6, a photocurable composition was prepared by uniformly mixing the same solute component concentration as in Example 19, to prepare a cured film having a thickness of 80 μm. Moreover, the protective coating layer with a thickness of 3 micrometers was formed in both surfaces of a 75-micrometer-thick base film, respectively, and the laminated film was produced. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was Δ, the surface roughness was 2.0 nm, and the haze was 0.25%.

  From Example 16 to Example 20, it was found that by adding the component (E) in the range of not less than 9.0 wt% and not more than 15.0 wt%, an excellent antiblocking function can be obtained. Further, it was found from Examples 19, 21 and 22 that when the thickness of the protective coating layer is 1 μm or more and 3 μm or less, an excellent antiblocking function can be obtained.

5-2. Add component (E) to Example 2>
Example 2
As shown in Table 7, 24.3 wt% of component (A), 9.7 wt% of component (B), 25.0 wt% of component (C1) (UT5467), 38.0 wt% of component (C2) (UT5490), and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was は, the antiblocking function was x, the surface roughness was 0.5 nm, and the haze was 0.23%.

[Example 23]
As shown in Table 7, 22.6 wt% of component (A), 9.0 wt% of component (B), 23.3 wt% of component (C1) (UT5467), 35.3 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.8 wt% and component (E) 7.0 wt%, and a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was は, the antiblocking function was x, the surface roughness was 1.8 nm, and the haze was 0.23%.

[Example 24]
As shown in Table 7, 22.1 wt% of component (A), 8.8 wt% of component (B), 22.8 wt% of component (C1) (UT5467), 34.5 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.7 wt% and component (E) 9.0 wt%, and a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ○, the surface roughness was 3.3 nm, and the haze was 0.23%.

[Example 25]
As shown in Table 7, 21.6 wt% of component (A), 8.6 wt% of component (B), 22.3 wt% of component (C1) (UT5467), 33.8 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.7 wt% and component (E) 11.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ○, the surface roughness was 4.6 nm, and the haze was 0.24%.

[Example 26]
As shown in Table 7, 21.1 wt% of component (A), 8.4 wt% of component (B), 21.8 wt% of component (C1) (UT5467), 33.1 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.6 wt% and component (E) 13.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 6.0 nm, and the haze was 0.25%.

[Example 27]
As shown in Table 7, 20.6 wt% of component (A), 8.2 wt% of component (B), 21.3 wt% of component (C1) (UT5467), 32.3 wt% of component (C2) (UT5490), component A photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.6 wt% and component (E) 15.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 35%, and the Martens hardness of the cured film was 128 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 8.0 nm, and the haze was 0.36%.

[Example 28]
As shown in Table 7, the photocurable composition was prepared by uniformly mixing the same solute component concentration as in Example 26, to prepare a cured film having a thickness of 80 μm. Moreover, the 1-micrometer-thick protective coating layer was formed in both surfaces of a 75-micrometer-thick base film, respectively, and the laminated film was produced. The breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 6.4 nm, and the haze was 0.25%.

[Example 29]
As shown in Table 7, the photocurable composition was prepared by uniformly mixing the same solute component concentration as in Example 26, to prepare a cured film having a thickness of 80 μm. Moreover, the protective coating layer with a thickness of 3 micrometers was formed in both surfaces of a 75-micrometer-thick base film, respectively, and the laminated film was produced. The breaking elongation of the cured film was 37%, and the Martens hardness of the cured film was 118 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was Δ, the surface roughness was 2.0 nm, and the haze was 0.25%.

  Even when the component (E) is added to Example 2, the component (E) is added in the range of not less than 9.0 wt% and not more than 15.0 wt% as in the case of adding the component (E) to Example 1. It has been found that excellent anti-blocking function can be obtained. Moreover, it turned out that the outstanding anti blocking function is obtained because the thickness of a protective coating layer is one to 3 micrometer.

5-3. Add component (E) to Example 3>
[Example 3]
As shown in Table 8, 24.3 wt% of component (A), 9.7 wt% of component (B), 13.0 wt% of component (C1) (UT5467), 50.0 wt% of component (C2) (UT5490), and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was は, the antiblocking function was x, the surface roughness was 0.5 nm, and the haze was 0.23%.

[Example 30]
As shown in Table 8, 22.6 wt% of component (A), 9.0 wt% of component (B), 12.1 wt% of component (C1) (UT5467), 46.4 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.8 wt% and component (E) 7.0 wt%, and a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was は, the antiblocking function was x, the surface roughness was 2.3 nm, and the haze was 0.23%.

[Example 31]
As shown in Table 8, 22.1 wt% of component (A), 8.8 wt% of component (B), 11.8 wt% of component (C1) (UT5467), 45.5 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.7 wt% and component (E) 9.0 wt%, and a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ○, the surface roughness was 3.3 nm, and the haze was 0.23%.

[Example 32]
As shown in Table 8, 21.6 wt% of component (A), 8.6 wt% of component (B), 11.6 wt% of component (C1) (UT5467), 44.5 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.7 wt% and component (E) 11.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ○, the surface roughness was 4.6 nm, and the haze was 0.24%.

[Example 33]
As shown in Table 8, 21.1 wt% of component (A), 8.4 wt% of component (B), 11.3 wt% of component (C1) (UT5467), 43.6 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.6 wt% and component (E) 13.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 6.0 nm, and the haze was 0.25%.

[Example 34]
As shown in Table 8, 20.6 wt% of component (A), 8.2 wt% of component (B), 11.1 wt% of component (C1) (UT5467), 42.5 wt% of component (C2) (UT5490), component A photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.6 wt% and component (E) 15.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 48%, and the Martens hardness of the cured film was 110 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 8.0 nm, and the haze was 0.36%.

[Example 35]
As shown in Table 8, a photocurable composition was prepared by uniformly mixing the same solute component concentration as in Example 33 to prepare a cured film having a thickness of 80 μm. Moreover, the 1-micrometer-thick protective coating layer was formed in both surfaces of a 75-micrometer-thick base film, respectively, and the laminated film was produced. The breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 6.4 nm, and the haze was 0.25%.

[Example 36]
As shown in Table 8, a photocurable composition was prepared by uniformly mixing the same solute component concentration as in Example 33 to prepare a cured film having a thickness of 80 μm. Moreover, the protective coating layer with a thickness of 3 micrometers was formed in both surfaces of a 75-micrometer-thick base film, respectively, and the laminated film was produced. The breaking elongation of the cured film was 52%, and the Martens hardness of the cured film was 100 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was Δ, the surface roughness was 2.0 nm, and the haze was 0.25%.

  Even when the component (E) is added to Example 3, the component (E) is added in the range of not less than 9.0 wt% and not more than 15.0 wt% as in the case of adding the component (E) to Example 1. It has been found that excellent anti-blocking function can be obtained. Moreover, it turned out that the outstanding anti blocking function is obtained because the thickness of a protective coating layer is one to 3 micrometer.

5-4. Use of methacrylic aggregate with an average particle size of 20 nm>
As the component (E), an aggregate (M23, manufactured by CIK Nanotech Co., Ltd.) having an average particle diameter of 20 nm which was surface-treated with a silane coupling agent having a methacryl group was used. The same components as in Example 1 were used except for this.

[Example 37]
As shown in Table 9, 22.6 wt% of component (A), 9.0 wt% of component (B), 18.0 wt% of component (C1) (UT5467), 40.6 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.8 wt% and component (E) 7.0 wt%, and a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was は, the antiblocking function was x, the surface roughness was 1.8 nm, and the haze was 0.23%.

[Example 38]
As shown in Table 9, 22.1 wt% of component (A), 8.8 wt% of component (B), 17.7 wt% of component (C1) (UT5467), 39.6 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.7 wt% and component (E) 9.0 wt%, and a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ○, the surface roughness was 3.6 nm, and the haze was 0.23%.

[Example 39]
As shown in Table 9, 21.1 wt% of component (A), 8.4 wt% of component (B), 16.9 wt% of component (C1) (UT5467), 38.0 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.6 wt% and component (E) 13.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 4.2 nm, and the haze was 0.25%.

[Example 40]
As shown in Table 9, 20.6 wt% of component (A), 8.2 wt% of component (B), 16.5 wt% of component (C1) (UT5467), 37.1 wt% of component (C2) (UT5490), component A photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.6 wt% and component (E) 15.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 41%, and the Martens hardness of the cured film was 125 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The adhesion evaluation was ○, the antiblocking function was 機能, the surface roughness was 5.5 nm, and the haze was 0.36%.

[Example 41]
As shown in Table 9, the photocurable composition was prepared by uniformly mixing the solute component concentration same as that of Example 39 to prepare a cured film having a thickness of 80 μm. Moreover, the 1-micrometer-thick protective coating layer was formed in both surfaces of a 75-micrometer-thick base film, respectively, and the laminated film was produced. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was 、, the antiblocking function was ◎, the surface roughness was 5.1 nm, and the haze was 0.25%.

[Example 42]
As shown in Table 9, the photocurable composition was prepared by uniformly mixing the solute component concentration same as that of Example 39 to prepare a cured film having a thickness of 80 μm. Moreover, the protective coating layer with a thickness of 3 micrometers was formed in both surfaces of a 75-micrometer-thick base film, respectively, and the laminated film was produced. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was Δ, the surface roughness was 2.0 nm, and the haze was 0.25%.

  From Examples 37 to 40, it was found that by adding the component (E) in the range of 9.0 wt% or more and 15.0 wt% or less, an excellent antiblocking function was obtained. Further, it was found from Examples 39, 41 and 42 that when the thickness of the protective coating layer is 1 μm or more and 3 μm or less, an excellent antiblocking function can be obtained. That is, it was found that even when a methacrylic aggregate having an average particle diameter of 20 nm was added as the component (E), an excellent antiblocking function was obtained.

5-5. Use of methacrylic aggregate having an average particle size of 30 nm>
As the component (E), an aggregate (M06, manufactured by CIK Nanotech Co., Ltd.) having an average particle diameter of 30 nm which was surface-treated with a silane coupling agent having a methacryl group was used. The same components as in Example 1 were used except for this.

[Example 43]
As shown in Table 10, 22.6 wt% of component (A), 9.0 wt% of component (B), 18.0 wt% of component (C1) (UT5467), 40.6 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.8 wt% and component (E) 7.0 wt%, and a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), the anti blocking function was x, surface roughness was 1.6 nm, and the haze was 0.23%.

[Example 44]
As shown in Table 10, 22.1 wt% of component (A), 8.8 wt% of component (B), 17.7 wt% of component (C1) (UT5467), 39.6 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.7 wt% and component (E) 9.0 wt%, and a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ○, the surface roughness was 2.5 nm, and the haze was 0.23%.

[Example 45]
As shown in Table 10, 21.1 wt% of component (A), 8.4 wt% of component (B), 16.9 wt% of component (C1) (UT5467), 38.0 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.6 wt% and component (E) 13.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 4.3 nm, and the haze was 0.25%.

[Example 46]
As shown in Table 10, 20.6 wt% of component (A), 8.2 wt% of component (B), 16.5 wt% of component (C1) (UT5467), 37.1 wt% of component (C2) (UT5490), component A photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.6 wt% and component (E) 15.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 41%, and the Martens hardness of the cured film was 125 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The adhesion evaluation was ○, the antiblocking function was 機能, the surface roughness was 5.5 nm, and the haze was 0.36%.

[Example 47]
As shown in Table 10, by mixing uniformly at the same solute component concentration as in Example 45, a photocurable composition was prepared, and a cured film having a thickness of 80 μm was produced. Moreover, the 1-micrometer-thick protective coating layer was formed in both surfaces of a 75-micrometer-thick base film, respectively, and the laminated film was produced. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 5.4 nm, and the haze was 0.25%.

[Example 48]
As shown in Table 10, by mixing uniformly at the same solute component concentration as in Example 45, a photocurable composition was prepared, and a cured film having a thickness of 80 μm was produced. Moreover, the protective coating layer with a thickness of 3 micrometers was formed in both surfaces of a 75-micrometer-thick base film, respectively, and the laminated film was produced. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was Δ, the surface roughness was 2.0 nm, and the haze was 0.25%.

  From Example 43 to Example 46, it was found that by adding the component (E) in the range of 9.0 wt% or more and 15.0 wt% or less, an excellent antiblocking function was obtained. Further, it was found from Examples 45, 47 and 48 that when the thickness of the protective coating layer is 1 μm or more and 3 μm or less, an excellent antiblocking function can be obtained. That is, it was found that even when a methacrylic aggregate having an average particle diameter of 30 nm was added as the component (E), an excellent antiblocking function was obtained.

5-6. Use of methacrylic aggregate with an average particle size of 40 nm>
As the component (E), an aggregate (M18, manufactured by CIK Nanotech Co., Ltd.) having an average particle diameter of 40 nm which was surface-treated with a silane coupling agent having a methacryl group was used. The same components as in Example 1 were used except for this.

[Example 49]
As shown in Table 11, 22.6 wt% of component (A), 9.0 wt% of component (B), 18.0 wt% of component (C1) (UT5467), 40.6 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.8 wt% and component (E) 7.0 wt%, and a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was は, the antiblocking function was x, the surface roughness was 1.7 nm, and the haze was 0.23%.

[Example 50]
As shown in Table 11, 22.1 wt% of component (A), 8.8 wt% of component (B), 17.7 wt% of component (C1) (UT5467), 39.6 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.7 wt% and component (E) 9.0 wt%, and a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ○, the surface roughness was 2.6 nm, and the haze was 0.23%.

[Example 51]
As shown in Table 11, 21.1 wt% of component (A), 8.4 wt% of component (B), 16.9 wt% of component (C1) (UT5467), 38.0 wt% of component (C2) (UT5490), component The photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.6 wt% and component (E) 13.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 4.8 nm, and the haze was 0.25%.

[Example 52]
As shown in Table 11, 20.6 wt% of component (A), 8.2 wt% of component (B), 16.5 wt% of component (C1) (UT5467), 37.1 wt% of component (C2) (UT5490), component A photocurable composition was prepared by uniformly mixing the solute component concentration of (D) 2.6 wt% and component (E) 15.0 wt% to prepare a cured film having a thickness of 80 μm. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film. The elongation at break of the cured film was 41%, and the Martens hardness of the cured film was 125 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The adhesion evaluation was ○, the antiblocking function was 機能, the surface roughness was 5.5 nm, and the haze was 0.36%.

[Example 53]
As shown in Table 11, the photocurable composition was prepared by uniformly mixing the solute component concentration the same as that of Example 51 to prepare a cured film having a thickness of 80 μm. Moreover, the 1-micrometer-thick protective coating layer was formed in both surfaces of a 75-micrometer-thick base film, respectively, and the laminated film was produced. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 5.5 nm, and the haze was 0.25%.

Example 54
As shown in Table 11, the photocurable composition was prepared by uniformly mixing the solute component concentration the same as that of Example 51 to prepare a cured film having a thickness of 80 μm. Moreover, the protective coating layer with a thickness of 3 micrometers was formed in both surfaces of a 75-micrometer-thick base film, respectively, and the laminated film was produced. The elongation at break of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was ○, the antiblocking function was Δ, the surface roughness was 2.0 nm, and the haze was 0.25%.

  From Example 49 to Example 52, it was found that by adding the component (E) in the range of not less than 9.0 wt% and not more than 15.0 wt%, an excellent antiblocking function can be obtained. Further, it was found from Examples 51, 53 and 54 that when the thickness of the protective coating layer is 1 μm or more and 3 μm or less, an excellent antiblocking function can be obtained. That is, it was found that even when a methacrylic aggregate having an average particle diameter of 40 nm was added as the component (E), an excellent antiblocking function was obtained.

5-7. Type of Component (E), Particle Size>
Silica sol with a mean particle diameter of 15 nm (MEK-ST (silica sol dispersed in methyl ethyl ketone), manufactured by Nissan Chemical Industries, Ltd.) as component (E1), a silane cup having a methacryl group with a mean particle diameter of 30 nm as component (E2) Dispersion surface-treated with a ring agent (H83, manufactured by CIK Nanotech Co., Ltd.), dispersion (E83, CIK Nanotech (E3N), surface-treated with a silane coupling agent having an alkyl group with an average particle diameter of 30 nm as component (E3) Co., Ltd., an aggregate (H94, manufactured by CIK Nanotech Co., Ltd.) surface-treated with a silane coupling agent having an alkyl group having an average particle diameter of 30 nm as the component (E4), an average particle diameter as the component (E5) 50 nm silica sol (MEK-STL (silica sol dispersed in methyl ethyl ketone), Nissan Chemical Industries ( Made as a component (E6), silica sol having an average particle diameter of 50 nm (IPA-STL (silica sol dispersed in isopropyl alcohol), Nissan Chemical Industries, Ltd., as a component (E7), methacrylic having an average particle diameter of 100 nm Dispersion surface-treated with a silane coupling agent having a group (E65, manufactured by CIK Nanotech Co., Ltd.), dispersion (surface-treated with a silane coupling agent having an alkyl group having an average particle diameter of 100 nm) as component (E8) H86, manufactured by CIK Nanotech Co., Ltd., an aggregate (K26, manufactured by Co., Ltd.) surface-treated with a silane coupling agent having a methacryl group having an average particle diameter of 100 nm as the component (E9) Silica sol having an average particle diameter of 100 nm (IPA-ST-ZL (silica sol dispersed in isopropyl alcohol) ), Manufactured by Nissan Chemical Industries), as component (E11), having an average particle size of 100nm silica sol (MEK-ST-ZL (silica sol dispersed in methyl ethyl ketone) was used Nissan Chemical Industries, Ltd.). The same components as in Example 1 were used except for this.

  Moreover, 21.1 wt% of component (A), 8.4 wt% of component (B), 16.9 wt% of component (C1) (UT5467), 38.0 wt% of component (C2) (UT5490), component (D) 2. A photocurable composition was prepared by uniformly mixing a solute component concentration of 6 wt% and component (E) 13.0 wt%, and a cured film having a thickness of 80 μm was produced. In addition, a protective coating layer having a thickness of 2 μm was formed on both sides of a 75 μm-thick base film, to produce a laminated film.

[Example 55]
As shown in Table 12, when the component (E1) was added, the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was は, the antiblocking function was x, the surface roughness was 0.6 nm, and the haze was 0.23%.

[Example 56]
As shown in Table 12, when the component (E2) was added, the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was は, the antiblocking function was x, the surface roughness was 1.1 nm, and the haze was 0.25%.

[Example 57]
As shown in Table 12, when the component (E3) was added, the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was 密 着, the antiblocking function was x, the surface roughness was 2.0 nm, and the haze was 0.25%.

[Embodiment 58]
As shown in Table 12, when the component (E4) and the dispersant were added, the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was x, the antiblocking function was ○, the surface roughness was 2.9 nm, and the haze was 0.25%.

[Example 59]
As shown in Table 12, when the component (E5) was added, the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was は, the antiblocking function was x, the surface roughness was 0.8 nm, and the haze was 0.23%.

[Example 60]
As shown in Table 12, when the component (E6) was added, the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was は, the antiblocking function was x, the surface roughness was 0.8 nm, and the haze was 0.23%.

[Example 61]
As shown in Table 12, when the component (E7) was added, the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was x, the antiblocking function was x, the surface roughness was 0.9 nm, and the haze was 0.24%.

[Example 62]
As shown in Table 12, when the component (E8) was added, the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was x, the antiblocking function was x, the surface roughness was 0.9 nm, and the haze was 0.24%.

[Example 63]
As shown in Table 12, when the component (E9) was added, the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. Further, the evaluation of adhesion was ○, the antiblocking function was x, the surface roughness was 1.0 nm, and the haze was 0.25%.

[Example 64]
As shown in Table 12, when the component (E10) was added, the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. Further, the evaluation of adhesion was ○, the antiblocking function was x, the surface roughness was 0.8 nm, and the haze was 0.27%.

[Example 65]
As shown in Table 12, when adding the component (E11), the breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the good number of times of high-speed flexibility of the laminated film was 10, the evaluation of the abrasion resistance of the laminated film by the steel wool was ○, and the evaluation of the abrasion resistance of the laminated film by the alcohol swab was ○. The evaluation of adhesion was 密 着, the antiblocking function was x, the surface roughness was 0.8 nm, and the haze was 0.26%.

  It was found that an excellent antiblocking function was obtained by adding inorganic fine particles in the form of aggregates having an average particle size of 10 nm or more and 50 nm or less. In addition, it was found that the surface treatment with a silane coupling agent having an alkyl group or a (meth) acryloyl group enhances the affinity and binding property with the binder component and provides an excellent anti-blocking function. .

11 base film, 12 protective coating layer, 13 laminated film, 14 transparent electrode, 15A, 15B laminated film for touch panel, 16 optical adjustment layer

Claims (12)

Trifunctional or higher (meth) acrylate monomers,
A difunctional (meth) acrylate monomer,
Polyether urethane (meth) acrylate oligomers,
Containing a photopolymerization initiator,
The content of the trifunctional or higher functional (meth) acrylate monomer is 5 to 50% by mass,
The content of the bifunctional (meth) acrylate monomer is 5 to 50% by mass,
The content of the polyether urethane (meth) acrylate oligomer is 40 to 80% by mass,
A photocurable composition having a breaking elongation at a thickness of 80 μm of 35% or more when photopolymerized. The photocurable composition according to claim 1, wherein the Martens hardness at a thickness of 80 μm when photopolymerized is 100 N / mm ² or more.   The photocurable composition according to claim 1 or 2, wherein the breaking elongation is 60% or less.   The photocurable composition according to any one of claims 1 to 3, wherein the photopolymerization initiator is an acetophenone photopolymerization initiator.   The photocurable composition according to any one of claims 1 to 4, containing inorganic fine particles which are aggregates of an average particle diameter of 10 nm to 50 nm.   The photocurable composition according to claim 5, wherein the inorganic fine particles are surface-treated with a silane coupling agent having an alkyl group or a (meth) acryloyl group. A base film made of a cyclic olefin resin,
And a protective coating layer formed on at least one side of the substrate film,
The protective coating layer contains a trifunctional or higher (meth) acrylate monomer, a difunctional (meth) acrylate monomer, a polyether urethane (meth) acrylate oligomer, and a photopolymerization initiator, and the trifunctional The content of the above (meth) acrylate monomer is 5 to 50% by mass, and the content of the bifunctional (meth) acrylate monomer is 5 to 50% by mass, and the polyether-based urethane (meth) the content of acrylate oligomer, a 40 to 80 wt%, the breaking elongation in the thickness 80μm upon photopolymerization, Ri Na photocurable composition is 35% or more by photopolymerization,
The laminated film whose thickness of the said protective coating layer is 1 micrometer or more and 4 micrometers or less . The laminated film according to claim 7, wherein the Martens hardness at a thickness of 80 μm when the photocurable composition is photopolymerized is 100 N / mm ² or more.   The laminated film according to claim 7, wherein the breaking elongation is 60% or less. The laminated film for touchscreens in which the transparent electrode is formed in the at least single side | surface of the laminated film of any one of Claims 7 thru | or 9 . The image display input device provided with the laminated film for touch panels of Claim 10 , and an image display element. A trifunctional or higher (meth) acrylate monomer, a difunctional (meth) acrylate monomer, a polyether urethane (meth) acrylate oligomer, and a photopolymerization initiator, and the trifunctional or higher (meth) acrylate The content of the monomer is 5 to 50% by mass, the content of the bifunctional (meth) acrylate monomer is 5 to 50% by mass, the content of the polyether-based urethane (meth) acrylate oligomer is And 40 to 80% by mass, and a photocurable composition having a breaking elongation of 35% or more at a thickness of 80 μm when photopolymerized is applied to at least one surface of a base film made of a cyclic olefin resin Process,
Forming a protective coating layer having a thickness of 1 μm or more and 4 μm or less on at least one surface of a substrate film by photopolymerizing the photocurable composition.

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