WO2016017799A1

WO2016017799A1 - Photocurable composition, and layered film

Info

Publication number: WO2016017799A1
Application number: PCT/JP2015/071794
Authority: WO
Inventors: 健太郎石川
Original assignee: デクセリアルズ株式会社
Priority date: 2014-08-01
Filing date: 2015-07-31
Publication date: 2016-02-04
Also published as: JP6505994B2; JP2016035013A; TW201619704A

Abstract

Provided are a photocurable composition with which excellent flexibility can be achieved, and a layered film. A photocurable composition, which includes a (meth)acrylate monomer that is at least trifunctional, a bifunctional (meth)acrylate monomer, a urethane (meth)acrylate oligomer including a polyether-based urethane (meth)acrylate oligomer, and a photopolymerization initiator, and in which the addition average value of the oligomer elongation of the urethane (meth)acrylate oligomer at a thickness of 80 µm after photopolymerization is at least 80%, is photopolymerized on a base-material film (11) to form protective coating layers (12).

Description

Photocurable composition and laminated film

The present invention relates to a photocurable composition particularly suitable for a protective coating layer laminated on at least one surface of a base film made of a cyclic olefin resin, and a laminated film. This application claims priority on the basis of Japanese Patent Application No. 2014-158250 filed on Aug. 1, 2014 in Japan. This application is incorporated herein by reference. Incorporated.

In recent years, a cyclic olefin resin film excellent in high transparency, low hygroscopicity, and refractive index stability has been used as a base film material for an electrode film for a touch panel (see, for example, Patent Document 1). A cyclic olefin-based resin film is preferable in terms of characteristics such as transparency and hygroscopicity, but it cannot be said to have sufficient flexibility. Further, 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 the cyclic olefin resin film is performed.

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

JP 2012-66477 A

The present invention has been proposed in view of such a conventional situation, and provides a photocurable composition and a laminated film capable of obtaining excellent flexibility.

As a result of intensive studies, the present inventor uses an urethane (meth) acrylate oligomer containing a polyether-based urethane (meth) acrylate oligomer, and adds an oligomer elongation when the urethane (meth) acrylate oligomer is photopolymerized. It has been found that a laminated film having excellent flexibility can be obtained by setting the average value to a predetermined value or more.

That is, the photocurable composition according to the present invention is a urethane (meth) acrylate containing a tri- or higher-functional (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, and a polyether-based urethane (meth) acrylate oligomer. It contains an oligomer and a photopolymerization initiator, and the additive average value of the oligomer elongation at a thickness of 80 μm when the urethane (meth) acrylate oligomer is photopolymerized is 80% or more.

Moreover, the laminated film according to the present invention includes a base film made of a cyclic olefin resin, and a protective coat layer formed on at least one surface of the base film, and the protective coat layer has a trifunctional or higher functionality ( A urethane (meth) acrylate containing a (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, a urethane (meth) acrylate oligomer including a polyether-based urethane (meth) acrylate oligomer, and a photopolymerization initiator. It is characterized by photopolymerizing a photocurable composition having an additive average value of oligomer elongation at a thickness of 80 μm when the oligomer is photopolymerized, of 80% or more.

Moreover, the manufacturing method of the laminated | multilayer film based on this invention is a urethane (meth) acrylate containing the (meth) acrylate monomer more than trifunctional, a bifunctional (meth) acrylate monomer, and a polyether-type urethane (meth) acrylate oligomer. A photocurable composition containing an oligomer and a photopolymerization initiator, wherein the additive average value of the degree of oligomer elongation at a thickness of 80 μm when the urethane (meth) acrylate oligomer is photopolymerized is 80% or more, Having a coating step of applying to at least one side of a base film made of a cyclic olefin-based resin, and a forming step of photopolymerizing the photocurable composition to form a protective coating layer on at least one side of the base film. Features.

According to the present invention, a urethane (meth) acrylate oligomer containing a polyether-based urethane (meth) acrylate oligomer is used, and an additive average value of the oligomer elongation when the urethane (meth) acrylate oligomer is photopolymerized is a predetermined value or more. By doing so, a laminated film having excellent flexibility can be obtained.

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. 1. Photocurable composition Laminated film 3. Manufacturing method of laminated film First Example 5 Second embodiment

<1. Photocurable composition>
The photocurable composition 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. Light of urethane (meth) acrylate oligomer (component (C)) containing urethane (meth) acrylate oligomer (component (C)) containing a (meth) acrylate oligomer and a photopolymerization initiator (component (D)) The additive average value of the oligomer elongation at a thickness of 80 μm when polymerized is 80% or more.

In addition, in this specification, (meth) acrylate is meant to include acrylic acid ester (acrylate) and methacrylic acid ester (methacrylate). Moreover, the additive average value of the oligomer elongation of a component (C) can be defined by a following formula.
Additive average value (%) of oligomer elongation of component (C) = Σ [(oligomer elongation (%)) × (ratio (%) in component (C)) / 100]

[Component (A): Trifunctional or higher functional (meth) acrylate monomer]
A component (A) is for improving the adhesiveness with cyclic olefin resin, and the reactivity of photocurable composition itself. Such a component (A) is a polymerizable compound having 3 or more acrylate residues or methacrylate residues (hereinafter referred to as (meth) acrylate residues) in the molecule, and is used in the field of adhesives and the like. A tri- or more functional (meth) acrylate monomer can be appropriately selected and used.

Specific examples of component (A) include pentaerythritol triacrylate (PETA), 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-converted triacrylate, ε-caprolactone modified tris-(-2 acryloxy) Ethyl) isocyanurate, trimethylolpropane triacrylate (TMPTA), ε-caprolactone modified tris (acryloxyethyl) acrylate, ethoxylated (20) trimethylolpropane triacrylate, propoxylated (3) trimethylolpropane triacrylate, propoxylated (6) Trimethylolpropane triacrylate, ethoxylated (9) Trimethylolpropane triacrylate, propoxylated (3) glyceryl triacrylate, ethoxylated (4) penta Examples include erythritol tetraacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate (DPHA), and the like, and one or more of these can be used. Among these, pentaerythritol triacrylate can be preferably used in terms of adhesion, reactivity, crosslinkability, surface hardness, and the like. Specific examples available on the market include the product name “M305” of Toagosei Co., Ltd. and the product name “TMM-3L” of Shin-Nakamura Chemical Co., Ltd.

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 curl. Therefore, the content is preferably 5 to 50% by mass, more preferably 15 to 40% by mass.

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

Specific examples of component (B) include dimethylol-tricyclodecane diacrylate, bisphenol AEO-modified diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, propoxylated bisphenol A diacrylate, tri 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 cyclohexanedimethanol 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 conversion diacrylate, etc. 1 type or 2 types or more can be used. Among these, dimethylol-licyclodecane diacrylate can be preferably used from the viewpoints of adhesion, reactivity, crosslinkability, surface hardness, and the like. Specific examples available on the market include Kyoeisha Chemical Co., Ltd. trade name “DCP-A”.

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 curl. Therefore, the content is preferably 5 to 50% by mass, more preferably 5 to 15% by mass.

[Component (C): Urethane (meth) acrylate oligomer]
Component (C) is a urethane (meth) acrylate oligomer containing at least a polyether-based urethane (meth) acrylate oligomer, and more preferably contains two or more polyether-based urethane (meth) acrylate oligomers. By including two or more kinds of polyether urethane (meth) acrylate oligomers, excellent scratch resistance can be obtained.

The polyether-based urethane (meth) acrylate oligomer is a compound having a unit derived from a polyether polyol compound, a polymerizable (meth) acryloyl group, and a urethane bond in the molecule. The polyether-based urethane (meth) acrylate oligomer is, for example, a (meth) acrylate having a hydroxyl group in a terminal isocyanate urethane prepolymer obtained by reacting a polyether polyol compound (X) and a polyvalent isocyanate compound (Y). Obtained by reacting (Z).

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

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), tetramethylxylylene diisocyanate (m-TMXDI), isophorone Diisocyanate (IPDI), norbornene diisocyanate (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane H6XDI), and the like.

Examples of the (meth) acrylate (Z) having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 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 polyether urethane (meth) acrylate oligomers available on the market include Nippon Synthetic Chemical Industry's trade names “UT5490”, “UT5467”, “UT5489”, “UT5522”, “UT5523”, “UT5495”, “UT5496”, “UT5497”, “UT5506” and the like can be mentioned.

As the component (C) other than the polyether-based urethane (meth) acrylate oligomer, a polyester-based urethane (meth) acrylate oligomer in which polyester glycol is chain-extended with diisocyanate and both ends thereof are (meth) acrylated, polyester glycol Instead, a caprolactone-based urethane (meth) acrylate oligomer using caprolactone diol, a polycarbonate-based urethane (meth) acrylate oligomer using polycarbonate diol instead of polyester glycol, and the like can be given. *

The additive average value of the degree of oligomer growth of the component (C) is 80% or more. Thereby, it becomes possible to obtain the excellent flexibility of the laminated film. Additivity average value of the degree of oligomer growth of an ingredient (C) can be defined by a following formula.
Additive average value (%) of oligomer elongation of component (C) = Σ [(oligomer elongation (%)) × (ratio (%) in component (C)) / 100]

The oligomer elongation (breaking elongation) of the polyether-based urethane (meth) acrylate oligomer of component (C) is preferably 5 to 300%. Moreover, when a component (C) contains 2 or more types of polyether type urethane (meth) acrylate oligomers, it is preferable that at least 1 type of oligomer elongation is 200% or more. The oligomer elongation is determined by drying a composition obtained by blending 100 parts by mass of component (C) and 3 parts by mass of 2-hydroxy-2-cyclohexylacetophenone as a photopolymerization initiator with a bar coater. After coating to a thickness of 80 μm, photopolymerization was performed under irradiation conditions of 300 mJ / cm ² , and this cured film (test piece: 70 mm × 20 mm) was subjected to a tensile tester (product name: Tensilon) by a method in accordance with JISK7127. , Orientec Co., Ltd.) and tensile rate at a rate of 0.5 mm / min, which can be shown as the elongation percentage (%) when the test piece is cut (broken). In addition, when the solvent contains 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 deteriorate, and if it is too large, the scratch resistance tends to deteriorate, preferably 40 to 80% by mass, More preferably, it is 55 to 70% by mass.

[Component (D): Photopolymerization initiator]
As component (D), it can select from a well-known radical photopolymerization initiator suitably, and can use it. Examples of the component (D) include acetophenone photopolymerization initiators, benzyl ketal photopolymerization initiators, phosphorus photopolymerization initiators, and the like, and one or more of these can be used.

Specific examples of the component (D) available on the market include 2-hydroxy-2-cyclohexylacetophenone (IRGACURE 184, manufactured by BASF Japan), α-hydroxy-α, α'-dimethylacetophenone (DAROCUR 1173, manufactured by BASF Japan), 2,2-dimethoxy-2-phenylacetophenone (IRGACURE 651, manufactured by BASF Japan), 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone (DAROCUR 2959, manufactured by BASF Japan), 2-hydroxy-1- {4- [2-hydroxy-2-methyl-propionyl] -benzyl} phenyl} -2 -Methyl group Pan-1-one (IRGACURE (IRGACURE) 127, manufactured by BASF Japan Ltd.) and the like. Examples of benzyl ketal photopolymerization initiators include benzophenone, fluorenone, dibenzosuberone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 4-hydroxybenzophenone, 4-chlorobenzophenone, 4,4′-dichlorobenzophenone, etc. Is mentioned. As phosphorous photopolymerization initiators, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE 819, manufactured by BASF Japan), (2,4,6-trimethylbenzoyl-diphenylphosphine) And oxide (DAROCURE TPO, manufactured by BASF Japan Ltd.), etc. Among these, it is preferable to use an acetophenone-based photopolymerization initiator from the viewpoint of realizing smooth photocuring.

If the content of the component (D) in the photocurable composition is too small, there is a tendency that the adhesiveness is decreased due to the decrease in hardness performance or the hardness is insufficient. Since it tends to decrease, the content is preferably 0.5 to 25% by mass, more preferably 1 to 10% by mass.

[Other ingredients]
In addition to the components (A) to (D) described above, the photocurable composition preferably further contains inorganic fine particles (component (E)) as necessary. Thereby, adjustment of a refractive index and the surface can be roughened, and antiblocking performance can be improved.

Component (E) includes fine metal oxide particles such as silicon oxide (silica), aluminum oxide, and zirconium oxide. In addition, it is preferable that the surface treatment is performed with a coupling agent or the like, and in particular, the surface treatment is performed with a silane coupling agent having an alkyl group or a (meth) acryloyl group in order to improve the affinity and binding property with the binder component. It is preferable that

Specific examples of the component (E) available on the market include trade names manufactured by CIK Nanotech Co., Ltd .: M23, H83, E83, M06, M44, H94, M18, E65, H58, K26, Nissan Chemical Industries, Ltd. Product 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 size of 10 nm to 50 nm. By using the aggregate, it is possible to prevent a micro-order particle size and to suppress an increase in haze. In addition, the average particle diameter of the component (E) is an image of visual observation or image from a secondary electron emission image photograph obtained by scanning electron microscope (SEM) or the like in the case of an aggregate of primary particles. It can be obtained by processing or measuring with a particle size distribution meter using a dynamic light scattering method, a static light scattering method or the like. In addition, the average particle diameter here refers to the number average particle diameter. Moreover, when a particle is not spherical, it means 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 it is too large, the haze tends to increase. Therefore, the content is preferably 7 to 15% by mass. The content is preferably 9 to 13% by mass.

In addition, the photocurable composition contains additives such as a solvent, a leveling agent, a hue adjusting agent, a colorant, an ultraviolet absorber, an antistatic agent, and various thermoplastic resin materials as long as the effects of the present invention are not impaired. 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. Examples of the material of the inorganic fine particles and the inorganic fine powder include a material mainly composed of a conductive metal oxide. 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.

Further, the photocurable composition is produced by uniformly mixing the above-described components (A) to (D), and further, 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 when photopolymerized, of 15% or more, more preferably 35% or more. Further, the breaking elongation is preferably 60% or less. Thereby, excellent flexibility and scratch resistance can be obtained. Further, 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.

Such a photocurable composition is particularly useful as a composition of a protective coat layer formed on at least one surface of a base film made of a cyclic olefin resin, and in the flexibility test, the protective coat layer and the cyclic olefin The occurrence of cracks on the surface of the resin film can be suppressed. Moreover, since it is excellent also in abrasion resistance, it can utilize preferably for a touchscreen 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 surface of the base film, and the protective coat layer is a trifunctional or higher functional (meta). An acrylate monomer (component (A)), a bifunctional (meth) acrylate monomer (component (B)), and a urethane (meth) acrylate oligomer (component (C)) including a polyether-based urethane (meth) acrylate oligomer; And an addition average value of the degree of oligomer elongation at a thickness of 80 μm when the photopolymerization of a urethane (meth) acrylate oligomer (component (C)) is carried out, containing a photopolymerization initiator (component (D)), 80% or more The photocurable composition is a photopolymerization.

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

The base film 11 is formed by forming a cyclic olefin resin into a sheet shape. As the cyclic olefin-based resin, a resin (COP) having a cycloolefin as a monomer and having an alicyclic structure obtained by ring-opening metathesis polymerization of a cyclic olefin (for example, norbornenes) and subsequent hydrogenation reaction, Examples thereof include a resin (COC) obtained by addition polymerization of a cyclic olefin (for example, norbornenes) and an α-olefin (for example, ethylene).

Specific examples of COP include polytetracyclododecene identified by the trade name “ZEONOR” of Nippon Zeon Co., Ltd. Specific examples of COC include ethylene norbornene copolymer identified by the trade name “TOPAS” of TOPAS Advanced Polymers, and ethylene tetracyclododecene identified by the trade name “APEL” of Mitsui Chemicals, Inc. -Methacrylic acid ester copolymer, etc. can be mentioned. A retardation function may be imparted to the film made of these cyclic olefin resins by a known method.

The thickness of the base film 11 varies depending on the type and performance of the optical device to which it is applied, but is usually 25 to 200 μm, preferably 40 to 150 μm. Further, the elongation at break of the base film 11 at a thickness of 80 μm 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 coat layer 12 is obtained by photopolymerizing the photocurable composition described above. The thickness of the protective coat layer 12 is usually 0.5 to 8 μm, preferably 0.8 to 7 μm. The protective coat layer 12 may be laminated only on one side of the base film 11.

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

2 and 3 are sectional views showing an example of a laminated film for a touch panel. A laminated film for touch panel 15 </ b> A shown in FIG. 2 has a protective coating layer 12 formed on both surfaces of a substrate film 11, and a known transparent electrode 14 such as ITO is formed on the surface of the protective coating layer 12. In the laminated film 15B for a touch panel shown in FIG. 3, an optical adjustment layer 16 such as a known retardation film is formed between the protective coat layer 12 and the transparent electrode 14.

Thus, by forming a transparent electrode using an ITO film, conductive fine particles, nanowire-shaped material, or the like on at least one surface of the laminated film as described above, it can be preferably used as a laminated film for a touch panel. Furthermore, by laminating such a laminated 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 for a smart phone or a personal computer.

<3. Manufacturing method of 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. Light of urethane (meth) acrylate oligomer (component (C)) containing urethane (meth) acrylate oligomer (component (C)) containing a (meth) acrylate oligomer and a photopolymerization initiator (component (D)) An application step of applying a photocurable composition having an additive average value of oligomer elongation at a thickness of 80 μm when polymerized to 80% or more to at least one surface of a base film made of a cyclic olefin resin; and photocuring And forming a protective coating layer on at least one surface of the base film.

Hereinafter, the adjustment process for adjusting the photocurable composition, the pretreatment process for pretreating the base film, the coating process for applying the photocurable composition, and the forming process for forming the protective coating layer will be described. .

[Adjustment process]
First, in addition to the components (A) to (D) described above, if necessary, a photocurable composition containing inorganic fine particles (component (E)) is used according to a conventional method using a stirrer such as a disper. Mix and adjust evenly. This photo-curable composition is preferably not only having translucency, but also having a hue that does not significantly change the hue of transmitted light and the amount of transmitted light due to coloring and haze.

The solvent is not particularly limited as long as it sufficiently dissolves the 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, and glycol ether solvents. Can be mentioned.

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

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

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

Drying conditions are not particularly limited, and may be natural drying or artificial drying that adjusts drying humidity, drying time, and the like. However, when wind is applied to the surface of the paint at the time of drying, it is preferable not to generate a wind pattern on the surface of the coating film. This is because, when a wind pattern is generated, the coating appearance is deteriorated and the surface thickness is uneven.

In addition, as rays for curing the photocurable composition, energy rays such as gamma rays, alpha rays, and electron beams can be applied in addition to ultraviolet rays. Moreover, it can manufacture according to the manufacturing method of this laminated film also about the manufacturing method of the laminated film for touch panels.

<4. First Example>
In the first embodiment, a tri- 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 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 in both surfaces of the base film, the laminated film was produced, and the high-speed flexibility of the laminated film and the scratch resistance were evaluated. The present invention is not limited to these examples.

Measurement of elongation at break, measurement of Martens hardness, production 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 breaking elongation]
After applying the photocurable composition to the peeled PET film with a bar coater, the photocurable composition was photopolymerized under irradiation conditions 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 rate of 0.5 mm / min using a tensile tester (product name: Tensilon, Orientec Co., Ltd.) by a method according to JISK7127, and the test piece is cut. Elongation rate was determined when (breaking). Practically, it is desired that the breaking elongation of the cured film is 35% or more.

Further, the elongation at break of each of the components (A) to (C) was measured in the same manner. A composition obtained by blending 100 parts by mass of the component to be measured and 3 parts by mass of 2-hydroxy-2-cyclohexylacetophenone as a photopolymerization initiator into the peeled PET film so that the thickness after drying with a bar coater is 80 μm. after coating, the photopolymerized by irradiation conditions of 300 mJ / cm ^2, the cured film (test piece: 70 mm × 20 mm), and by a method according to JISK7127, a tensile tester (product name: Tensilon, Orientec Co. ) To obtain an elongation percentage (%) when the test piece was cut (ruptured) at a speed of 0.5 mm / min. 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]
After applying the photocurable composition to the peeled PET film with a bar coater, the photocurable composition was photopolymerized under irradiation conditions 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 the slide glass with Aron Alpha manufactured by Toagosei Co., Ltd. The surface hardness was measured with a Vickers indenter so that an arbitrary place 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 meter (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 thinly as possible.

[Production of laminated film]
As a base film, a 75 μm-thick cyclic olefin resin film subjected to corona treatment (a film obtained by dispersing about 10% of a styrene-based elastomer in a COC resin with respect to the resin component, and the elongation at break is MD The direction and TD direction were less than 6%). After apply | coating a photocurable composition on both surfaces of this base film, it photopolymerized on the irradiation conditions of 300 mJ / cm < ² >, respectively, formed the protective coating layer on both surfaces of the base film, and obtained the laminated | multilayer film.

[Evaluation of high-speed flexibility of laminated film]
Bending operation of bending the laminated film (test piece: 100 m × 20 mm) in one direction in the MD (Machine Direction) direction of the base film is performed at 10 locations at a rate of 60 times per minute, and the presence or absence of cracks on the base film surface Was observed with an optical microscope having a magnification of 10 times. And the bending location where a crack is not observed at all was counted as favorable. Although it depends on the application, it is desirable that the number of good high-speed flexibility of the laminated film is 7 or more.

[Evaluation of scratch resistance of laminated film]
A laminated film (test piece: 100 mm x 50 mm) is attached to a scratch tester (product name: Gakushin type friction fastness tester, Tester Sangyo Co., Ltd.), a load of 250 g is added to # 0000 steel wool, and the hardened layer surface Was scratched 20 times (10 reciprocations), and the presence or absence of scratches was visually observed. A case where no scratch was observed was evaluated as “good”, and a case where a scratch was observed was evaluated as “bad”.

A laminated film (test piece: 100 mm × 50 mm) is attached to a scratch tester (product name: Gakushin type friction fastness tester, Tester Sangyo Co., Ltd.), a load of 250 g is applied to an alcohol swab, and the surface of the hardened layer is applied. The scratch test was performed 20 times (10 reciprocations), and the presence or absence of scratches was visually observed. A case where no scratch was observed was evaluated as “good”, and a case where a scratch was observed was evaluated as “bad”.

<4-1. Relationship between additive average value of oligomer elongation of component (C) and high-speed flexibility 1>
[Example 1]
Trifunctional or higher functional (meth) acrylate monomer (component (A)), pentaerythritol triacrylate (M-305, manufactured by Toagosei Co., Ltd.), bifunctional (meth) acrylate monomer (component (B)) Tricyclodecane dimethanol diacrylate (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.), urethane (meth) acrylate oligomer (component (C1)), polyether-based urethane having 10 functional groups and 9% oligomer elongation As an oligomer (UT5467, manufactured by Nippon Synthetic Chemical Co., Ltd.) and a urethane (meth) acrylate oligomer (component (C2)), a polyether urethane oligomer (UT5490, Nippon Synthetic Chemical Co., Ltd.) having 2 functional groups and an oligomer elongation of 250% )), A photopolymerization initiator (component (D)) as 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, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 19.4 wt%, component (C2) (UT5490) 43.6 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 2]
As shown in Table 1, the same components as in Example 1 were used, and component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 25.0 wt%, component (C2 ) (UT5490) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 38.0 wt% and component (D) 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.4%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 3]
As shown in Table 1, the same components as in Example 1 were used, and component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 13.0 wt%, component (C2 ) (UT5490) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 50.0 wt% and component (D) 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.3%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 4]
As shown in Table 1, the same components as in Example 1 were used, and component (A) 20.8 wt%, component (B) 8.3 wt%, component (C1) (UT5467) 20.9 wt%, component (C2 ) (UT5490) 47.0 wt% and component (D) were uniformly mixed at a solute component concentration of 3.0 wt% to prepare a photocurable composition, and a cured film having a thickness of 80 µm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 5]
As shown in Table 1, the same components as in Example 1 were used, and component (A) 27.7 wt%, component (B) 11.1 wt%, component (C1) (UT5467) 17.9 wt%, component (C2 ) (UT5490) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 40.3 wt% and component (D) 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.9%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 39%, and the Martens hardness of the cured film was 119 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 6]
As shown in Table 1, the same components as in Example 1 were used, and component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 8.0 wt%, component (C2 ) (UT5490) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 55.0 wt% and component (D) 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 219.4%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 61%, and the Martens hardness of the cured film was 94 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of scratch resistance by steel wool of the laminated film was x, and the evaluation of scratch resistance by alcohol swab of the laminated film was x.

[Example 7]
As shown in Table 1, the same components as in Example 1 were used, and component (A) 17.3 wt%, component (B) 6.9 wt%, component (C1) (UT5467) 22.4 wt%, component (C2 ) (UT5490) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 50.4 wt% and component (D) 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 56%, and the Martens hardness of the cured film was 95 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of scratch resistance by steel wool of the laminated film was x, and the evaluation of scratch resistance by alcohol swab of the laminated film was x.

[Example 8]
As shown in Table 1, the same components as in Example 1 were used, and component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 29.1 wt%, component (C2 ) (UT5490) 33.9 wt% and component (D) A photocurable composition was prepared by mixing uniformly at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 µm was produced. Additivity average value of the degree of oligomer growth of an ingredient (C) was 138.7%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 31%, and the Martens hardness of the cured film was 140 N / mm ² . In addition, the number of good high-speed flexibility of the laminated film was 8, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 9]
As shown in Table 1, the same components as in Example 1 were used, and component (A) 31.2 wt%, component (B) 12.5 wt%, component (C1) (UT5467) 16.4 wt%, component (C2 ) (UT5490) 36.9 wt% and component (D) 3.0 wt% solute component concentration was uniformly mixed to prepare a photocurable composition, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 34%, and the Martens hardness of the cured film was 134 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 7, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

As in Examples 1 to 9, when the additive average value of the degree of oligomer elongation of the component (C) was 80% or more, good evaluation results of high-speed flexibility were obtained. Further, it was found that when the Martens hardness was 100 N / mm ² or more as in Examples 1 to 5, 8, and 9, good scratch resistance (steel wool, alcohol swab) was obtained.

<4-2. Relationship between Additive Average Value of Oligomer Elongation of Component (C) and High-Speed Flexibility 2>
Next, the type of the component (C) was changed, and the relationship between the additive average value of the oligomer elongation of the component (C) and the high-speed flexibility was verified. As a component (C1), a polyether urethane oligomer (UT5467, manufactured by Nippon Synthetic Chemical Co., Ltd.) having 10 functional groups and an oligomer elongation of 9%. Ether-based urethane oligomer (UT5490, manufactured by Nippon Synthetic Chemical Co., Ltd.), component (C3), polyether-based urethane oligomer (UT5489, manufactured by Nippon Synthetic Chemical Co., Ltd.), component having 6 functional groups and 34% oligomer elongation As (C4), a polyether urethane oligomer (UT5506, Nippon Synthetic Chemical Co., Ltd.) having 10 functional groups and 39% oligomer elongation was used. Other than these, the same components as in Example 1 were used.

[Example 10]
As shown in Table 2, component (A) 24.0 wt%, component (B) 10.0 wt%, component (C1) (UT5467) 19.0 wt%, component (C2) (UT5490) 44.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 177.3%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 11]
As shown in Table 2, component (A) 24.0 wt%, component (B) 10.0 wt%, component (C1) (UT5467) 33.0 wt%, component (C2) (UT5490) 30.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 123.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 20%, and the Martens hardness of the cured film was 150 N / mm ² . In addition, the number of good high-speed flexibility of the laminated film was 8, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 12]
As shown in Table 2, component (A) 24.0 wt%, component (B) 10.0 wt%, component (C1) (UT5467) 33.0 wt%, component (C2) (UT5490) 30.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 85.5%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 15%, and the Martens hardness of the cured film was 160 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 7, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 13]
As shown in Table 2, component (A) 24.0 wt%, component (B) 10.0 wt%, component (C3) (UT5489) 19.0 wt%, component (C2) (UT5490) 44.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 184.9%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 51%, and the Martens hardness of the cured film was 100 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 14]
As shown in Table 2, component (A) 24.0 wt%, component (B) 10.0 wt%, component (C2) (UT5490) 44.0 wt%, component (C4) (UT5506) 19.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 186.4%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 55%, and the Martens hardness of the cured film was 95 N / mm ² . The number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was x, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 15]
As shown in Table 2, component (A) 29.0 wt%, component (B) 12.0 wt%, component (C1) (UT5467) 20.0 wt%, component (C2) (UT5490) 36.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 163.9%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 30%, and the Martens hardness of the cured film was 140 N / mm ² . In addition, the number of good high-speed flexibility of the laminated film was 8, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

In Examples 10 to 15, as in Examples 1 to 19, since the additive average value of the degree of oligomer elongation of the component (C) was 80% or more, good high-speed flexibility evaluation results were obtained.

<4-3. Relationship between additive average value of oligomer elongation of component (C) and high-speed flexibility 3>
Next, as a component (C1), a polyether urethane oligomer (UT5467, manufactured by Nippon Synthetic Chemical Co., Ltd.) having 10 functional groups and an oligomer elongation of 9%, and as a component (C2), having 2 functional groups and an oligomer elongation of 250. % Polyether urethane oligomer (UT5490, manufactured by Nippon Synthetic Chemical Co., Ltd.) As component (C3), polyether urethane oligomer (UT5489, manufactured by Nippon Synthetic Chemical Co., Ltd.) having 6 functional groups and an oligomer elongation of 34% ), Polyether urethane oligomer (UT5522, manufactured by Nippon Synthetic Chemical Co., Ltd.) having 5 functional groups and 72% oligomer elongation as component (C4), 4 functional groups and 110% oligomer elongation as component (C5) Polyether urethane oligomer (UT5523, manufactured by Nippon Synthetic Chemical Co., Ltd.), component (C6), functional group 10. Polyether urethane oligomer (UT5595, manufactured by Nippon Synthetic Chemical Co., Ltd.) having an oligomer elongation of 16%, and a polyether urethane oligomer (UT5596, Japan) having 10 functional groups and 13% oligomer elongation. As a component (C8), a polyether urethane oligomer (UT5597, manufactured by Nippon Synthetic Chemical Co., Ltd.) having 10 functional groups and an oligomer elongation of 50%, and a component (C9) A polyether urethane oligomer (UT5506, manufactured by Nippon Synthetic Chemical Co., Ltd.) having a group number of 10 and an oligomer elongation of 39% was used. Other than these, the same components as in Example 1 were used.

[Comparative Example 1]
As shown in Table 3, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 19.4 wt%, component (C3) (UT5489) 43.6 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 26.3%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 11%, and the Martens hardness of the cured film was 214 N / mm ² . The number of good high-speed flexibility of the laminated film was 2, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Comparative Example 2]
As shown in Table 3, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 19.4 wt%, component (C4) (UT5522) 43.6 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 52.6%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 14%, and the Martens hardness of the cured film was 199 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 4, the evaluation of the abrasion resistance of the laminated film with steel wool was ○, and the evaluation of the abrasion resistance of the laminated film with an alcohol swab was x.

[Comparative Example 3]
As shown in Table 3, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 19.4 wt%, component (C5) (UT5523) 43.6 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 78.9%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 18%, and the Martens hardness of the cured film was 183 N / mm ² . The number of good high-speed flexibility of the laminated film was 5, the evaluation of the abrasion resistance of the laminated film with steel wool was ○, and the evaluation of the abrasion resistance of the laminated film with an alcohol swab was x.

[Comparative Example 4]
As shown in Table 3, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 19.4 wt%, component (C6) (UT5595) 43.6 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 13.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 10%, and the Martens hardness of the cured film was 222 N / mm ² . The number of good high-speed flexibility of the laminated film was 0, the evaluation of the scratch resistance of the laminated film with steel wool was ◯, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ◯.

[Comparative Example 5]
As shown in Table 3, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 19.4 wt%, component (C7) (UT5596) 43.6 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 11.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 10%, and the Martens hardness of the cured film was 223 N / mm ² . The number of good high-speed flexibility of the laminated film was 0, the evaluation of the scratch resistance of the laminated film with steel wool was ◯, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ◯.

[Comparative Example 6]
As shown in Table 3, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 19.4 wt%, component (C8) (UT5597) 43.6 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 37.4%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 12%, and the Martens hardness of the cured film was 208 N / mm ² . Further, the number of good times of the high-speed flexibility of the laminated film was 1, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was x.

[Comparative Example 7]
As shown in Table 3, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 19.4 wt%, component (C9) (UT5506) 43.6 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 29.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 11%, and the Martens hardness of the cured film was 212 N / mm ² . The number of good high-speed flexibility of the laminated film was 2, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Comparative Example 8]
As shown in Table 3, the solute component of component (A) 24.3 wt%, component (B) 9.7 wt%, component (C4) (UT5522) 63.0 wt%, and component (D) 3.0 wt% A photocurable composition was prepared by mixing uniformly at a concentration to prepare a cured film having a thickness of 80 μm. Additivity average value of the degree of oligomer growth of an ingredient (C) was 72.0%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare 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 . Further, the number of good high-speed flexibility of the laminated film was 4, the evaluation of the abrasion resistance of the laminated film with steel wool was ○, and the evaluation of the abrasion resistance of the laminated film with an alcohol swab was x.

[Example 16]
As shown in Table 3, the solute component of component (A) 24.3 wt%, component (B) 9.7 wt%, component (C5) (UT5523) 63.0 wt%, and component (D) 3.0 wt% A photocurable composition was prepared by mixing uniformly at a concentration to prepare a cured film having a thickness of 80 μm. Additivity average value of the degree of oligomer growth of an ingredient (C) was 110.0%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 24%, and the Martens hardness of the cured film was 164 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 7, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was x.

[Example 17]
As shown in Table 3, the solute component of component (A) 24.3 wt%, component (B) 9.7 wt%, component (C2) (UT5590) 63.0 wt%, and component (D) 3.0 wt% A photocurable composition was prepared by mixing uniformly at a concentration to prepare a cured film having a thickness of 80 μm. Additivity average value of the degree of oligomer growth of an ingredient (C) was 250.0%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 86%, and the Martens hardness of the cured film was 82 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was x.

[Comparative Example 9]
As shown in Table 3, the solute component of component (A) 24.3 wt%, component (B) 9.7 wt%, component (C8) (UT5523) 63.0 wt%, and component (D) 3.0 wt% A photocurable composition was prepared by mixing uniformly at a concentration to prepare a cured film having a thickness of 80 μm. Additivity average value of the degree of oligomer growth of an ingredient (C) was 50.0%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 14%, and the Martens hardness of the cured film was 200 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 6, the evaluation of scratch resistance by steel wool of the laminated film was ○, and the evaluation of scratch resistance by alcohol swab of the laminated film was x.

As in Comparative Examples 1 to 9, when the additive average value of the degree of oligomer elongation of the component (C) was less than 80%, good high-speed flexibility evaluation results could not be obtained. On the other hand, even when one kind of polyether-based urethane (meth) acrylate oligomer was used as in Examples 16 and 17, when the oligomer elongation was 80% or more, a good high-speed flexibility evaluation result was obtained. .

In addition, as in Comparative Examples 1 to 9, when a polyether urethane oligomer having an oligomer elongation of less than 100% was used as the component (C), good high-speed flexibility evaluation results could not be obtained. On the other hand, when a polyether urethane oligomer having an oligomer elongation of 100% or more was used as in Examples 1, 16, and 17, good high-speed flexibility evaluation results were obtained.

<4-4. Regarding Relationship between Components (A) to (C) and High-Speed Flexibility>
Next, when the component (A) or the component (B) is not blended, the high-speed flexibility when the polyether urethane oligomer is not blended as the component (C) was verified. As component (B1), tricyclodecane dimethanol diacrylate (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.), as component (B2), isocyanuric acid EO-converted diacrylate (M215, manufactured by Toagosei Co., Ltd.), component (CO1) is a caprolactone-based urethane oligomer (UT5236) with 9 functional groups and an oligomer elongation of 35%, and the component (CO2) is a urethane acrylate oligomer (UV7605, Nippon Synthetic Chemical) with 6 functional groups and an oligomer elongation of 0.8%. (Manufactured by Co., Ltd.), as component (D1), 2-hydroxy-1- {4- [2-hydroxy-2-methyl-propionyl] -benzyl} phenyl} -2-methyl-propan-1-one (Irgacure ( IRGACURE) 127, manufactured by BASF Japan Ltd.) and 2-Hydro as component (D2) Shi-2-cyclohexyl-acetophenone was used (IRGACURE (IRGACURE) 184, manufactured by BASF Japan Ltd.). Other than these, the same components as in Example 1 were used.

[Comparative Example 10]
As shown in Table 4, without adding the component (B), the component (A) 34.0 wt%, the component (C1) (UT5467) 19.4 wt%, the component (C2) (UT5490) 43.6 wt%, And the photocurable composition was prepared by mixing uniformly by the solute component density | concentration of component (D2) 3.0 wt%, and the 80-micrometer-thick cured film was produced. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 6, the evaluation of the abrasion resistance of the laminated film with steel wool was x, and the evaluation of the abrasion resistance of the laminated film with an alcohol swab was ○.

[Comparative Example 11]
As shown in Table 4, without blending component (A), component (B1) 34.0 wt%, component (C1) (UT5467) 19.4 wt%, component (C2) (UT5490) 43.6 wt%, And the photocurable composition was prepared by mixing uniformly by the solute component density | concentration of component (D2) 3.0 wt%, and the 80-micrometer-thick cured film was produced. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 35%, and the Martens hardness of the cured film was 118 N / mm ² . The number of good high-speed flexibility of the laminated film was 5, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Comparative Example 12]
As shown in Table 4, the component (A) is 9.7 wt%, the component (B2) is 29.1 wt%, the component (CO1) is 58.2 wt%, and the component (D1) is 3.0 wt% and the solute component concentration is uniform. Were mixed to prepare a photocurable composition, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 35.0%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 20%, and the Martens hardness of the cured film was 160 N / mm ² . The number of good high-speed flexibility of the laminated film was 4, the evaluation of the scratch resistance of the laminated film with steel wool was ◯, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ◯.

[Comparative Example 13]
As shown in Table 4, the component (A) is 9.7 wt%, the component (B2) is 38.8 wt%, the component (CO1) is 48.5 wt%, and the component (D1) is 3.0 wt% and the solute component concentration is uniform. Were mixed to prepare a photocurable composition, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 35.0%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare 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 . The number of good high-speed flexibility of the laminated film was 2, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Comparative Example 14]
As shown in Table 4, the component (A) is 9.7 wt%, the component (B2) is 48.5 wt%, the component (CO1) is 38.8 wt%, and the component (D1) is 3.0 wt% and the solute component concentration is uniform. Were mixed to prepare a photocurable composition, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 35.0%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 13%, and the Martens hardness of the cured film was 194 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 1, the evaluation of the scratch resistance of the laminated film with steel wool was ◯, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ◯.

[Comparative Example 15]
As shown in Table 4, component (A) 9.7 wt%, component (B2) 29.1 wt%, component (CO1) 19.4 wt%, component (CO2) 38.8 wt%, and component (D1) 3 A photocurable composition was prepared by uniformly mixing at a solute component concentration of 0.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 12.2%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 5%, and the Martens hardness of the cured film was 206 N / mm ² . The number of good high-speed flexibility of the laminated film was 0, the evaluation of the scratch resistance of the laminated film with steel wool was ◯, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ◯.

[Comparative Example 16]
As shown in Table 4, component (A) 9.7 wt%, component (B2) 29.1 wt%, component (CO1) 29.1 wt%, component (CO2) 29.1 wt%, and component (D1) 3 A photocurable composition was prepared by uniformly mixing at a solute component concentration of 0.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 17.9%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 7%, and the Martens hardness of the cured film was 194 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 1, the evaluation of the scratch resistance of the laminated film with steel wool was ◯, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ◯.

[Comparative Example 17]
As shown in Table 4, component (A) 9.7 wt%, component (B2) 29.1 wt%, component (CO1) 38.8 wt%, component (CO2) 19.4 wt%, and component (D1) 3 A photocurable composition was prepared by uniformly mixing at a solute component concentration of 0.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 23.6%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 10%, and the Martens hardness of the cured film was 182 N / mm ² . The number of good high-speed flexibility of the laminated film was 2, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

When either component (A) or component (B) is not added as in Comparative Examples 10 and 11, even when the additive average value of the oligomer elongation of the component (C) is 80% or more, An evaluation result of good high-speed flexibility was not obtained. In addition, as in Comparative Examples 12 to 17, when a caprolactone urethane oligomer or a polyfunctional urethane acrylate oligomer is used as the component (C) without blending a polyether urethane oligomer, good high-speed flexibility can be obtained. Evaluation results could not be obtained.

<4-5. Relationship between component (D) and high-speed flexibility>
Next, the relationship between component (D) and high-speed flexibility was verified. As component (D1), 2-hydroxy-1- {4- [2-hydroxy-2-methyl-propionyl] -benzyl} phenyl} -2-methyl-propan-1-one (IRGACURE 127, BASF Japan 2-hydroxy-2-cyclohexylacetophenone (IRGACURE 184, manufactured by BASF Japan) was used as the component (D2). Other than these, the same components as in Example 1 were used.

[Example 18]
As shown in Table 5, component (A) 24.5 wt%, component (B) 9.8 wt%, component (C1) (UT5467) 19.6 wt%, component (C2) (UT5490) 44.1 wt%, and Then, a photocurable composition was prepared by uniformly mixing the component (D1) at a solute component concentration of 2.0 wt% to prepare a cured film having a thickness of 80 μm. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . The number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was x, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 19]
As shown in Table 5, component (A) 24.0 wt%, component (B) 9.6 wt%, component (C1) (UT5467) 19.2 wt%, component (C2) (UT5490) 43.2 wt%, and Then, a photocurable composition was prepared by uniformly mixing the component (D1) at a solute component concentration of 4.0 wt% to prepare a cured film having a thickness of 80 μm. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 20]
As shown in Table 5, component (A) 23.8 wt%, component (B) 9.5 wt%, component (C1) (UT5467) 19.0 wt%, component (C2) (UT5490) 42.8 wt%, and Then, a photocurable composition was prepared by uniformly mixing the component (D1) at a solute component concentration of 5.0 wt% to prepare a cured film having a thickness of 80 μm. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 21]
As shown in Table 5, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 19.4 wt%, component (C2) (UT5490) 43.6 wt%, and Then, a photocurable composition was prepared by uniformly mixing the component (D2) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . The number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was x, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

As in Examples 1 and 18 to 20, good high-speed flexibility evaluation results were obtained when the component (D1) was in the range of 2.0 wt% to 5.0 wt%. Moreover, even in the case of the component (D2) as in Example 21, a good evaluation result of high-speed flexibility was obtained. That is, it was found that by using an acetophenone photopolymerization initiator, an excellent evaluation result of high-speed flexibility can be obtained.

<4-6. Relationship between protective coating layer thickness and high-speed flexibility>
Next, the relationship between the film thickness of the protective coating layer and high-speed flexibility was verified. As the components (A) to (D), the same components as in Example 1 were used.

[Example 22]
As shown in Table 6, 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 prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 1 μm was formed on both surfaces of the 75 μm-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 23]
As shown in Table 6, 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 prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 3 μm was formed on both surfaces of the 75 μm-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 24]
As shown in Table 6, 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 prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 4 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○.

[Example 25]
As shown in Table 6, 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 prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 5 μm was formed on both surfaces of the 75 μm-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . In addition, the number of good high-speed flexibility of the laminated film was 8, the evaluation of scratch resistance by steel wool of the laminated film was x, and the evaluation of scratch resistance by alcohol swab of the laminated film was ○.

From Examples 1 and 22 to 25, it was found that good high-speed flexibility can be obtained when the thickness of the protective coating layer is 1 μm or more and 5 μm or less. It was also found that good scratch resistance was obtained when the thickness of the protective coating layer was 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. In the same manner as in the first example, the elongation at break and Martens hardness of the cured film obtained by photopolymerization of the photocurable composition were measured. Moreover, the cured layer which consists of a photocurable composition was formed in both surfaces of the base film, the laminated film was produced, and the high-speed flexibility of the laminated film and the scratch resistance were evaluated. Furthermore, the adhesiveness and anti-blocking function of the laminated film were evaluated, and the surface roughness and haze of the laminated film were measured. The present invention is not limited to these examples.

Adhesion evaluation, anti-blocking function evaluation, surface roughness measurement, and haze measurement were performed as follows.

[Evaluation of adhesion]
With respect to the protective coat layer of the laminated film (50 mm × 50 mm), a linear cut was made with a cutter to form 100 grids. When the adhesive tape (cellophane tape, Nichiban Co., Ltd.) was applied to the grid and peeled off, the number of grids remaining on the laminated film side without being transferred to the adhesive tape was counted. The case where the number was 100 was evaluated as “good”, the case where it was less than 100 and 30 or more was evaluated as “Δ”, 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, the laminated film in which the surfaces of the protective coat layers were adhered to each other was cut into a strip shape, a load (g) was applied to an adhesion area of 4 cm ² (2 cm × 2 cm), and the appearance state was defined as a blocking performance value. The case where the state of occurrence of Newton rings, which are adhesion marks 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 evaluated as “Δ”, and the case of less than 300 g was evaluated as “bad”.

[Measurement of surface roughness]
The surface roughness of the protective coating layer of the laminated film was measured using AFM (SPA400, manufactured by Hitachi High-Tech Science Co., Ltd.).

[Measurement of haze]
About a laminated | multilayer film, the haze was measured based on JISK7136 using the haze meter (HM150, product made by Murakami Color Research Laboratory).

<5-1. Addition of component (E) to Example 1>
Trifunctional or higher functional (meth) acrylate monomer (component (A)), pentaerythritol triacrylate (M-305, manufactured by Toagosei Co., Ltd.), bifunctional (meth) acrylate monomer (component (B)) Tricyclodecane dimethanol diacrylate (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.), urethane (meth) acrylate oligomer (component (C1)), polyether-based urethane having 10 functional groups and 9% oligomer elongation As an oligomer (UT5467, manufactured by Nippon Synthetic Chemical Co., Ltd.) and a urethane (meth) acrylate oligomer (component (C2)), a polyether urethane oligomer (UT5490, Nippon Synthetic Chemical Co., Ltd.) having 2 functional groups and an oligomer elongation of 250% 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.), (component (E)) with an alkyl group Aggregates (M44, manufactured by CIK Nanotech Co., Ltd.) having an average particle diameter of 30 nm, which was surface-treated with the silane coupling agent having, were used.

[Example 1]
As shown in Table 7, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 19.4 wt%, component (C2) (UT5490) 43.7 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.5 nm, and haze was 0.23%.

[Example 26]
As shown in Table 7, component (E) was added to the component of Example 1, component (A) 22.6 wt%, component (B) 9.0 wt%, component (C1) (UT5467) 18.0 wt%. A photo-curable composition was prepared by uniformly mixing the components (C2) (UT5490) 40.6 wt%, the component (D) 2.8 wt%, and the component (E) 7.0 wt%. Then, a cured film having a thickness of 80 μm was produced. Additivity average value of the degree of oligomer growth of an ingredient (C) was 176.0%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 2.0 nm, and haze was 0.23%.

[Example 27]
As shown in Table 7, the component (E) was added to the component of Example 1, the component (A) 22.1 wt%, the component (B) 8.8 wt%, the component (C1) (UT5467) 17.7 wt%. A photocurable composition was prepared by uniformly mixing the components (C2) (UT5490) 39.6 wt%, the component (D) 2.7 wt%, and the component (E) 9.0 wt% solute component concentrations. Then, a cured film having a thickness of 80 μm was produced. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.6%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 3.3 nm, and haze was 0.23%.

[Example 28]
As shown in Table 7, the component (E) was added to the component of Example 1, the component (A) 21.6 wt%, the component (B) 8.6 wt%, the component (C1) (UT5467) 17.3 wt%. A photo-curable composition was prepared by uniformly mixing the components (C2) (UT5490) 38.8 wt%, the component (D) 2.7 wt%, and the component (E) 11.0 wt%. Then, a cured film having a thickness of 80 μm was produced. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.7%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 4.6 nm, and haze was 0.24%.

[Example 29]
As shown in Table 7, component (E) was added to the component of Example 1, component (A) 21.1 wt%, component (B) 8.4 wt%, component (C1) (UT5467) 16.9 wt% A photo-curable composition was prepared by uniformly mixing the components (C2) (UT5490) 38.0 wt%, the component (D) 2.6 wt%, and the component (E) 13.0 wt%. Then, a cured film having a thickness of 80 μm was produced. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the anti-blocking function was ◎, the surface roughness was 6.0 nm, and the haze was 0.25%.

[Example 30]
As shown in Table 7, the component (E) was added to the component of Example 1, the component (A) 20.6 wt%, the component (B) 8.2 wt%, the component (C1) (UT5467) 16.5 wt%. A photocurable composition was prepared by uniformly mixing the components (C2) (UT5490) 37.1 wt%, the component (D) 2.6 wt%, and the component (E) 15.0 wt%. Then, a cured film having a thickness of 80 μm was produced. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 41%, and the Martens hardness of the cured film was 125 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the anti-blocking function was ◎, the surface roughness was 8.0 nm, and the haze was 0.36%.

[Example 31]
As shown in Table 7, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 29 to prepare a cured film having a thickness of 80 μm. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 1 μm was formed on both surfaces of the 75 μm-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 6.5 nm, and the haze was 0.25%.

[Example 32]
As shown in Table 7, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 29 to prepare a cured film having a thickness of 80 μm. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 3 μm was formed on both surfaces of the 75 μm-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, 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 26 to Example 30, it was found that an excellent antiblocking function can be obtained by adding the component (E) in the range of 9.0 wt% to 15.0 wt%. Moreover, from Examples 29, 31, and 32, it was found that an excellent antiblocking function can be obtained when the thickness of the protective coating layer is 1 μm or more and 3 μm or less.

<5-2. Addition of component (E) to Example 2>
[Example 2]
As shown in Table 8, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 25.0 wt%, component (C2) (UT5490) 38.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.4%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.5 nm, and haze was 0.23%.

[Example 33]
As shown in Table 8, component (A) 22.6 wt%, component (B) 9.0 wt%, component (C1) (UT5467) 23.3 wt%, component (C2) (UT5490) 35.3 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.8 wt% and component (E) 7.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.2%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 1.8 nm, and haze was 0.23%.

[Example 34]
As shown in Table 8, component (A) 22.1 wt%, component (B) 8.8 wt%, component (C1) (UT5467) 22.8 wt%, component (C2) (UT5490) 34.5 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.7 wt% and component (E) 9.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.1%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 3.3 nm, and haze was 0.23%.

[Example 35]
As shown in Table 8, component (A) 21.6 wt%, component (B) 8.6 wt%, component (C1) (UT5467) 22.3 wt%, component (C2) (UT5490) 33.8 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.7 wt% and component (E) 11.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.2%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 4.6 nm, and haze was 0.24%.

[Example 36]
As shown in Table 8, component (A) 21.1 wt%, component (B) 8.4 wt%, component (C1) (UT5467) 21.8 wt%, component (C2) (UT5490) 33.1 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 13.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.3%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the anti-blocking function was ◎, the surface roughness was 6.0 nm, and the haze was 0.25%.

[Example 37]
As shown in Table 8, component (A) 20.6 wt%, component (B) 8.2 wt%, component (C1) (UT5467) 21.3 wt%, component (C2) (UT5490) 32.3 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 15.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.2%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 35%, and the Martens hardness of the cured film was 128 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the anti-blocking function was ◎, the surface roughness was 8.0 nm, and the haze was 0.36%.

[Example 38]
As shown in Table 8, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 26, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.3%. Further, a protective coating layer having a thickness of 1 μm was formed on both surfaces of the 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the anti-blocking function was ◎, the surface roughness was 6.4 nm, and the haze was 0.25%.

[Example 39]
As shown in Table 8, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 26, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 154.3%. Further, a protective coating layer having a thickness of 3 μm was formed on both surfaces of the 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, 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 9.0 wt% to 15.0 wt% in the same manner as when the component (E) is added to Example 1. Thus, it was found that an excellent anti-blocking function can be obtained. It was also found that an excellent antiblocking function can be obtained when the thickness of the protective coating layer is 1 μm or more and 3 μm or less.

<5-3. Addition of component (E) to Example 3>
[Example 3]
As shown in Table 9, component (A) 24.3 wt%, component (B) 9.7 wt%, component (C1) (UT5467) 13.0 wt%, component (C2) (UT5490) 50.0 wt%, and The photocurable composition was prepared by uniformly mixing the component (D) at a solute component concentration of 3.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.3%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.5 nm, and haze was 0.23%.

[Example 40]
As shown in Table 9, component (A) 22.6 wt%, component (B) 9.1 wt%, component (C1) (UT5467) 12.1 wt%, component (C2) (UT5490) 46.4 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.8 wt% and component (E) 7.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.2%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 2.3 nm, and haze was 0.23%.

[Example 41]
As shown in Table 9, component (A) 22.1 wt%, component (B) 8.8 wt%, component (C1) (UT5467) 11.8 wt%, component (C2) (UT5490) 45.5 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.7 wt% and component (E) 9.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.4%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 3.3 nm, and haze was 0.23%.

[Example 42]
As shown in Table 9, component (A) 21.6 wt%, component (B) 8.6 wt%, component (C1) (UT5467) 11.6 wt%, component (C2) (UT5490) 44.5 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.7 wt% and component (E) 11.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.2%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 4.6 nm, and haze was 0.24%.

[Example 43]
As shown in Table 9, component (A) 21.1 wt%, component (B) 8.4 wt%, component (C1) (UT5467) 11.3 wt%, component (C2) (UT5490) 43.6 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 13.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.4%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the anti-blocking function was ◎, the surface roughness was 6.0 nm, and the haze was 0.25%.

[Example 44]
As shown in Table 9, component (A) 20.6 wt%, component (B) 8.2 wt%, component (C1) (UT5467) 11.1 wt%, component (C2) (UT5490) 42.5 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 15.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.1%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 48%, and the Martens hardness of the cured film was 110 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the anti-blocking function was ◎, the surface roughness was 8.0 nm, and the haze was 0.36%.

[Example 45]
As shown in Table 9, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 33 to prepare a cured film having a thickness of 80 μm. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.4%. Further, a protective coating layer having a thickness of 1 μm was formed on both surfaces of the 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the anti-blocking function was ◎, the surface roughness was 6.4 nm, and the haze was 0.25%.

[Example 46]
As shown in Table 9, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 33 to prepare a cured film having a thickness of 80 μm. Additivity average value of the degree of oligomer growth of an ingredient (C) was 200.4%. Further, a protective coating layer having a thickness of 3 μm was formed on both surfaces of the 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, 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 9.0 wt% to 15.0 wt% in the same manner as when the component (E) is added to Example 1. Thus, it was found that an excellent anti-blocking function can be obtained. It was also found that an excellent antiblocking function can be obtained when the thickness of the protective coating layer is 1 μm or more and 3 μm or less.

<5-4. Use of methacrylic aggregate having 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. Other than this, the same components as in Example 1 were used.

[Example 47]
As shown in Table 10, component (A) 22.6 wt%, component (B) 9.0 wt%, component (C1) (UT5467) 18.0 wt%, component (C2) (UT5490) 40.6 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.8 wt% and component (E) 7.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 176.0%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 1.8 nm, and haze was 0.23%.

[Example 48]
As shown in Table 10, component (A) 22.1 wt%, component (B) 8.8 wt%, component (C1) (UT5467) 17.7 wt%, component (C2) (UT5490) 39.6 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.7 wt% and component (E) 9.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.6%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 3.6 nm, and haze was 0.23%.

[Example 49]
As shown in Table 10, component (A) 21.1 wt%, component (B) 8.4 wt%, component (C1) (UT5467) 16.9 wt%, component (C2) (UT5490) 38.0 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 13.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the anti-blocking function was ◎, the surface roughness was 4.2 nm, and the haze was 0.25%.

[Example 50]
As shown in Table 10, component (A) 20.6 wt%, component (B) 8.2 wt%, component (C1) (UT5467) 16.5 wt%, component (C2) (UT5490) 37.1 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 15.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 41%, and the Martens hardness of the cured film was 125 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 5.5 nm, and the haze was 0.36%.

[Example 51]
As shown in Table 10, a photocurable composition was prepared by uniformly mixing at the same solute component concentration as in Example 49, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 1 μm was formed on both surfaces of the 75 μm-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the anti-blocking function was ◎, the surface roughness was 5.1 nm, and the haze was 0.25%.

[Example 52]
As shown in Table 10, a photocurable composition was prepared by uniformly mixing at the same solute component concentration as in Example 49, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 3 μm was formed on both surfaces of the 75 μm-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, 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 47 to 50, it was found that an excellent antiblocking function can be obtained by adding the component (E) in the range of 9.0 wt% to 15.0 wt%. Moreover, from Examples 49, 51, and 52, it was found that an excellent anti-blocking function was obtained when the thickness of the protective coating layer was 1 μm or more and 3 μm or less. 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 size of 30 nm, which was surface-treated with a silane coupling agent having a methacryl group, was used. Other than this, the same components as in Example 1 were used.

[Example 53]
As shown in Table 11, component (A) 22.6 wt%, component (B) 9.0 wt%, component (C1) (UT5467) 18.0 wt%, component (C2) (UT5490) 40.6 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.8 wt% and component (E) 7.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 176.0%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 1.6 nm, and haze was 0.23%.

[Example 54]
As shown in Table 11, component (A) 22.1 wt%, component (B) 8.8 wt%, component (C1) (UT5467) 17.7 wt%, component (C2) (UT5490) 39.6 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.7 wt% and component (E) 9.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.6%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 2.5 nm, and haze was 0.23%.

[Example 55]
As shown in Table 11, component (A) 21.1 wt%, component (B) 8.4 wt%, component (C1) (UT5467) 16.9 wt%, component (C2) (UT5490) 38.0 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 13.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 4.3 nm, and the haze was 0.25%.

[Example 56]
As shown in Table 11, component (A) 20.6 wt%, component (B) 8.2 wt%, component (C1) (UT5467) 16.5 wt%, component (C2) (UT5490) 37.1 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 15.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 41%, and the Martens hardness of the cured film was 125 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 5.5 nm, and the haze was 0.36%.

[Example 57]
As shown in Table 11, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 55, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 1 μm was formed on both surfaces of the 75 μm-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 5.4 nm, and the haze was 0.25%.

[Example 58]
As shown in Table 11, a photocurable composition was prepared by mixing uniformly at the same solute component concentration as in Example 55, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 3 μm was formed on both surfaces of the 75 μm-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, 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 53 to Example 56, it was found that an excellent antiblocking function can be obtained by adding component (E) in the range of 9.0 wt% to 15.0 wt%. Moreover, from Examples 55, 57, and 58, it was found that an excellent antiblocking function was obtained when the thickness of the protective coating layer was 1 μm or more and 3 μm or less. 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 having 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 that was surface-treated with a silane coupling agent having a methacryl group was used. Other than this, the same components as in Example 1 were used.

[Example 59]
As shown in Table 12, component (A) 22.6 wt%, component (B) 9.0 wt%, component (C1) (UT5467) 18.0 wt%, component (C2) (UT5490) 40.6 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.8 wt% and component (E) 7.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 176.0%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 1.7 nm, and haze was 0.23%.

[Example 60]
As shown in Table 12, component (A) 22.1 wt%, component (B) 8.8 wt%, component (C1) (UT5467) 17.7 wt%, component (C2) (UT5490) 39.6 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.7 wt% and component (E) 9.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.6%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function (circle), surface roughness was 2.6 nm, and haze was 0.23%.

[Example 61]
As shown in Table 12, component (A) 21.1 wt%, component (B) 8.4 wt%, component (C1) (UT5467) 16.9 wt%, component (C2) (UT5490) 38.0 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 13.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the anti-blocking function was ◎, the surface roughness was 4.8 nm, and the haze was 0.25%.

[Example 62]
As shown in Table 12, component (A) 20.6 wt%, component (B) 8.2 wt%, component (C1) (UT5467) 16.5 wt%, component (C2) (UT5490) 37.1 wt%, component (D) A photocurable composition was prepared by uniformly mixing at a solute component concentration of 2.6 wt% and component (E) 15.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film. The breaking elongation of the cured film was 41%, and the Martens hardness of the cured film was 125 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 5.5 nm, and the haze was 0.36%.

[Example 63]
As shown in Table 12, a photocurable composition was prepared by uniformly mixing at the same solute component concentration as in Example 61, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 1 μm was formed on both surfaces of the 75 μm-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was ○, the antiblocking function was ◎, the surface roughness was 5.5 nm, and the haze was 0.25%.

[Example 64]
As shown in Table 12, a photocurable composition was prepared by uniformly mixing at the same solute component concentration as in Example 61, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. Further, a protective coating layer having a thickness of 3 μm was formed on both surfaces of the 75 μm-thick base film to produce a laminated film. The breaking elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, 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 59 to Example 62, it was found that an excellent antiblocking function can be obtained by adding the component (E) in the range of 9.0 wt% to 15.0 wt%. Moreover, from Examples 61, 63, and 64, it was found that an excellent antiblocking function was obtained when the thickness of the protective coating layer was 1 μm or more and 3 μm or less. 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. About type and particle size of component (E)>
As component (E1), silica sol having an average particle size of 15 nm (MEK-ST (silica sol dispersed in methyl ethyl ketone), manufactured by Nissan Chemical Industries, Ltd.), and as component (E2), a silane cup having a methacryl group having an average particle size of 30 nm Dispersion surface-treated with a ring agent (H83, manufactured by CIK Nanotech Co., Ltd.) As component (E3), a dispersion treated with a silane coupling agent having an alkyl group with an average particle diameter of 30 nm (E83, CIK Nanotech ( Co., Ltd.), as component (E4), an aggregate (H94, manufactured by CIK Nanotech Co., Ltd.) surface-treated with a silane coupling agent having an alkyl group with an average particle size of 30 nm, and as component (E5), the average particle size 50 nm silica sol (MEK-STL (silica sol dispersed in methyl ethyl ketone), Nissan Chemical Industries ( )), As component (E6), silica sol having an average particle size of 50 nm (IPA-STL (silica sol dispersed in isopropyl alcohol), manufactured by Nissan Chemical Industries, Ltd.), and as component (E7), methacryl having an average particle size of 100 nm. Dispersion surface-treated with a silane coupling agent having a group (E65, manufactured by CIK Nanotech Co., Ltd.), and component (E8) having a surface treatment with a silane coupling agent having an alkyl group having an average particle diameter of 100 nm ( H86, manufactured by CIK Nanotech Co., Ltd.), and as component (E9), an aggregate (K26, manufactured by CIK Nanotech Co., Ltd.), component (E10) surface-treated with a silane coupling agent having a methacryl group having an average particle diameter of 100 nm Silica sol (IPA-ST-ZL (isopropyl alcohol) As a component (E11), silica sol having an average particle size of 100 nm (MEK-ST-ZL (silica sol dispersed in methyl ethyl ketone), manufactured by Nissan Chemical Industries, Ltd.) is used as the component (E11). did. Other than this, the same components as in Example 1 were used.

In addition, component (A) 21.1 wt%, component (B) 8.4 wt%, component (C1) (UT5467) 16.9 wt%, component (C2) (UT5490) 38.0 wt%, component (D) 2. A photocurable composition was prepared by uniformly mixing at a solute component concentration of 6 wt% and component (E) 13.0 wt%, and a cured film having a thickness of 80 μm was prepared. Additivity average value of the degree of oligomer growth of an ingredient (C) was 175.8%. In addition, a protective coating layer having a thickness of 2 μm was formed on both surfaces of the 75 μm-thick base film to prepare a laminated film.

[Example 65]
As shown in Table 13, the elongation at break of the cured film when the component (E1) was added was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.6 nm, and haze was 0.23%.

[Example 66]
As shown in Table 13, when the component (E2) was added, 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), the antiblocking function was x, surface roughness was 1.1 nm, and haze was 0.25%.

[Example 67]
As shown in Table 13, when the component (E3) was added, 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 2.0 nm, and haze was 0.25%.

[Example 68]
As shown in Table 13, the breaking elongation of the cured film when the component (E4) and the dispersant were added was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, the evaluation of adhesion was x, the anti-blocking function was ◯, the surface roughness was 2.9 nm, and the haze was 0.25%.

[Example 69]
As shown in Table 13, the elongation at break of the cured film when the component (E5) was added was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.8 nm, and haze was 0.23%.

[Example 70]
As shown in Table 13, when the component (E6) was added, 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.8 nm, and haze was 0.23%.

[Example 71]
As shown in Table 13, when the component (E7) was added, 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, 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 72]
As shown in Table 13, when the component (E8) was added, 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 number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Further, 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 73]
As shown in Table 13, the elongation at break of the cured film when the component (E9) was added was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 1.0 nm, and haze was 0.25%.

[Example 74]
As shown in Table 13, when the component (E10) was added, the fracture elongation of the cured film was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.8 nm, and haze was 0.27%.

[Example 75]
As shown in Table 13, the elongation at break of the cured film when the component (E11) was added was 45%, and the Martens hardness of the cured film was 115 N / mm ² . Further, the number of good high-speed flexibility of the laminated film was 10, the evaluation of the scratch resistance of the laminated film with steel wool was ○, and the evaluation of the scratch resistance of the laminated film with an alcohol swab was ○. Moreover, evaluation of adhesiveness was (circle), antiblocking function was x, surface roughness was 0.8 nm, and haze was 0.26%.

It was found that an excellent antiblocking function can be obtained by adding inorganic fine particles that are aggregates having an average particle diameter of 10 nm to 50 nm. Moreover, it was found that the surface treatment with the silane coupling agent having an alkyl group or a (meth) acryloyl group improves the affinity and binding properties with the binder component and provides an excellent antiblocking function. .

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

Claims

A tri- or higher functional (meth) acrylate monomer;
A bifunctional (meth) acrylate monomer;
Urethane (meth) acrylate oligomers including polyether-based urethane (meth) acrylate oligomers;
Containing a photopolymerization initiator,
A photocurable composition having an additive average value of oligomer elongation at a thickness of 80 μm when the urethane (meth) acrylate oligomer is photopolymerized is 80% or more.
The photocurable composition according to claim 1, wherein the urethane (meth) acrylate oligomer comprises two or more polyether-based urethane (meth) acrylate oligomers.
The photocurable composition according to claim 1 or 2, wherein the Martens hardness at a thickness of 80 µm when photopolymerized is 100 N / mm 2 or more.
The photocurable composition according to any one of claims 1 to 3, wherein a breaking elongation at a thickness of 80 µm when photopolymerized is 15% or more.
The photocurable composition according to any one of claims 1 to 4, wherein the elongation at break when the thickness is 80 µm when photopolymerized is 60% or less.
The photocurable composition according to any one of claims 1 to 5, wherein the photopolymerization initiator is an acetophenone photopolymerization initiator.
The photocurable composition according to any one of claims 1 to 6, comprising inorganic fine particles that are aggregates having an average particle diameter of 10 nm to 50 nm.
The photocurable composition according to claim 7, 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;
A protective coat layer formed on at least one side of the base film,
The protective coating layer includes a tri- or higher functional (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, a urethane (meth) acrylate oligomer including a polyether-based urethane (meth) acrylate oligomer, and a photopolymerization initiator. And a photopolymerizable photocurable composition having an additive average value of the degree of oligomer elongation at a thickness of 80 μm when the urethane (meth) acrylate oligomer is photopolymerized is 80% or more.
The laminated film according to claim 9, 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 9 or 10, wherein the elongation at break at a thickness of 80 µm when the photocurable composition is photopolymerized is 15% or more.
The laminated film according to any one of claims 9 to 11, wherein the breaking elongation at a thickness of 80 µm when the photocurable composition is photopolymerized is 60% or less.
The laminated film according to any one of claims 9 to 12, wherein a thickness of the protective coating layer is 1 µm or more and 4 µm or less.
A laminated film for a touch panel, wherein a transparent electrode is formed on at least one side of the laminated film according to any one of claims 9 to 13.
An image display input device comprising the laminated film for a touch panel according to claim 14 and an image display element.
Containing a tri- or higher functional (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, a urethane (meth) acrylate oligomer including a polyether-based urethane (meth) acrylate oligomer, and a photopolymerization initiator, On at least one side of a base film made of a cyclic olefin resin, a photocurable composition having an additive average value of oligomer elongation at a thickness of 80 μm when the urethane (meth) acrylate oligomer is photopolymerized is 80% or more. An application process to apply;
A method for producing a laminated film, comprising: a step of photopolymerizing the photocurable composition to form a protective coating layer on at least one surface of the base film.