WO2020067165A1 - Cover film - Google Patents

Cover film Download PDF

Info

Publication number
WO2020067165A1
WO2020067165A1 PCT/JP2019/037616 JP2019037616W WO2020067165A1 WO 2020067165 A1 WO2020067165 A1 WO 2020067165A1 JP 2019037616 W JP2019037616 W JP 2019037616W WO 2020067165 A1 WO2020067165 A1 WO 2020067165A1
Authority
WO
WIPO (PCT)
Prior art keywords
hard coat
coat layer
acrylate
meth
cover film
Prior art date
Application number
PCT/JP2019/037616
Other languages
French (fr)
Japanese (ja)
Inventor
隆太 斎藤
Original Assignee
グンゼ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by グンゼ株式会社 filed Critical グンゼ株式会社
Priority to JP2020506284A priority Critical patent/JP6733071B1/en
Publication of WO2020067165A1 publication Critical patent/WO2020067165A1/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

Definitions

  • the present invention relates to a cover film.
  • Patent Document 1 proposes a cover film having a base film and a hard coat layer formed on the surface of the base film.
  • the hard coat layer is required to have high hardness so that scratches and dents are not caused by external force.
  • abrasion resistance that does not cause abrasion is required.
  • such abrasion resistance cannot be dealt with simply by increasing the hardness of the hard coat layer.
  • the present invention has been made to solve the above problems, and has as its object to provide a cover film for a display, which has high hardness and can also improve scratch resistance.
  • Item 1 A transparent base film, A first hard coat layer laminated on at least one surface of the base film, An adhesive layer laminated on the first hard coat layer; A second hard coat layer laminated on the adhesive layer, having a smaller film thickness than the first hard coat layer, and containing a fluorine-based additive; With The surface pencil hardness of the first hard coat layer is 7H or more, The cover film, wherein the surface pencil hardness of the second hard coat layer is 2H or more and 6H or less.
  • the first hard coat layer is laminated on both sides of the base film, Item 2.
  • Item 3. The cover film according to item 1 or 2, wherein the first hard coat layer has a thickness of 5 to 50 ⁇ m.
  • Item 4. The cover film according to any one of Items 1 to 3, wherein the thickness of the second hard coat layer is 1 to 30 ⁇ m.
  • Item 5 The cover film according to any one of Items 1 to 4, wherein the first hard coat layer contains a branched fluorine-based additive.
  • the scratch resistance can be improved while having high hardness.
  • FIG. 1 is a sectional view of a cover film according to an embodiment of the present invention. As shown in FIG. 1, this cover film is laminated on a transparent substrate film 1, a first hard coat layer 2 laminated on both sides of the substrate film 1, and one first hard coat layer 2. And a second hard coat layer 4 laminated on the adhesive layer 3.
  • this cover film is laminated on a transparent substrate film 1, a first hard coat layer 2 laminated on both sides of the substrate film 1, and one first hard coat layer 2.
  • each member will be described in detail.
  • the substrate film 1 according to the present embodiment can be formed of various transparent materials, and can be formed of, for example, cellulose acylate, cycloolefin polymer, polycarbonate, acrylate polymer, polyester, polyimide, and the like.
  • Various additives can be added to the base film 1 as needed.
  • various additives such as a plasticizer, an antistatic agent, and an ultraviolet absorber may be added.
  • the thickness of the base film 1 is, for example, preferably 25 ⁇ m or more and 300 ⁇ m or less, more preferably 50 ⁇ m or more and 200 ⁇ m or less, and even more preferably 75 ⁇ m or more and 125 ⁇ m or less.
  • the thickness is less than 25 ⁇ m, sufficient surface hardness cannot be obtained on the surface of the second hard coat layer 4, and when the thickness is more than 300 ⁇ m, the productivity of the cover film decreases.
  • the first hard coat layer 2 is obtained by curing a first hard coat layer forming resin composition (hereinafter, simply referred to as a first composition) containing an ionizing radiation-curable resin, a photopolymerization initiator, and the like. Further, additives described later can be added to this composition as needed.
  • a first hard coat layer forming resin composition hereinafter, simply referred to as a first composition
  • the ionizing radiation-curable resin includes a compound having a radical polymerizability that is polymerized or cross-linked by ionizing radiation (ultraviolet rays or electron beams). For example, at least one ethylenically unsaturated bond is contained in a structural unit. Or a mixture thereof.
  • Examples of the monofunctional compound containing one unsaturated bond include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, n-butyl (meth) acrylate, glycidyl (meth) acrylate, and cyclohexyl ( (Meth) acrylate and the like.
  • bifunctional compound containing two unsaturated bonds examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and nonane.
  • polyfunctional compound containing three or more unsaturated bonds examples include, for example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, tris Tri (meth) acrylates such as 2-hydroxyethyl isocyanurate tri (meth) acrylate and glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate Trifunctional (meth) acrylate compounds such as acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol Trifunctional or higher polyfunctional (e.g., tri (meth
  • a urethane-based resin can be mixed with the (meth) acrylate compound.
  • a urethane (meth) acrylate resin can be used.
  • the urethane (meth) acrylate compound pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol Pentaacrylate, toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate isophorone diisocyanate urethane prepolymer, dipentaeryth
  • the molecular weight of the urethane resin is preferably from 1,000 to 10,000, more preferably from 2,000 to 5,000.
  • the term “molecular weight” used in the present specification means a weight average molecular weight measured by GPC using polystyrene as a standard polymer.
  • Photopolymerization initiator examples include benzyl methyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropane-1 ⁇ -hydroxy ketones such as 2-one, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino ⁇ -aminoketones such as phenyl) butanone-1, bisacylphosphine oxides such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and 2,2′-bis (o -Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,1'-biimidazole, bis (2,4,5-trif
  • iron arene complexes trihalogenomethyl-substituted S-triazines, sulfonium salts, diazonium salts, phosphonium salts, selenonium salts, arsonium salts, iodonium salts and the like can be mentioned.
  • iodonium salts Macromolecules, 10, 1307 (1977).
  • diphenyliodonium ditolyliodonium, phenyl (p-anisyl) iodonium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p ⁇ -chlorophenyl) iodonium and the like
  • an additive can be added to the first composition as needed.
  • a silicone-based or fluorine-based additive for example, a leveling agent
  • the first hard coat layer 2 since the first hard coat layer 2 is required to have a surface leveling property in order to laminate the adhesive layer 3, it is preferable that the first hard coat layer 2 contains an additive such as a fluorine-based additive (branched type).
  • the amount of these additives is not particularly limited, but is, for example, preferably 0.1 to 1.5 parts by weight, and more preferably 0.2 to 1.2 parts by weight based on 100 parts by weight of the first composition. Parts by weight, more preferably 0.3 to 1 part by weight.
  • silica fine particles can be mixed.
  • the silica fine particles are not particularly limited as long as they improve the hardness of the first hard coat layer 2, but it is preferable to use silica fine particles having a primary particle size of 5 to 100 nm, and a primary particle size of 10 to 100 nm. 80 nm silica fine particles are more preferred.
  • the amount of the silica fine particles is not particularly limited, but is, for example, preferably 20 to 50 parts by weight, more preferably 30 to 40 parts by weight, per 100 parts by weight of the first composition. This is because when less than 20 parts by weight, it is difficult to improve the pencil hardness, while when more than 50 parts by weight, the sliding resistance may be reduced.
  • the thickness of the first hard coat layer 2 is preferably 5 to 50 ⁇ m, more preferably 10 to 45 ⁇ m, and particularly preferably 20 to 40 ⁇ m. This is because if the thickness is less than 5 ⁇ m, the surface hardness of the cover film becomes insufficient. On the other hand, when the thickness is larger than 50 ⁇ m, the curing shrinkage of the cover film is increased, and the cover film is unfavorably curled due to shrinkage at the time of production.
  • the first hard coat layer 2 has a surface pencil hardness test defined by JIS 5600-5-4 (1999) of preferably 7H or more, more preferably 8H or more. Thereby, as described later, the surface hardness of the second hard coat layer 4 laminated on the first hard coat layer 2 can be improved.
  • the adhesive layer 3 is not particularly limited as long as the adhesive layer 3 can bond the first and second hard coat layers 1 and 2, and examples thereof include polyurethane, polyacryl, polyester, epoxy, and polyvinyl acetate.
  • An adhesive such as a polyvinyl chloride / vinyl acetate copolymer or a cellulose-based adhesive can be appropriately used.
  • the thickness of the adhesive layer 3 is preferably, for example, 0.1 to 10 ⁇ m, more preferably 0.5 to 7 ⁇ m, and still more preferably 1 to 5 ⁇ m.
  • the second hard coat layer 4 is obtained by curing a second hard coat layer forming resin composition (hereinafter, simply referred to as a second composition) containing an ionizing radiation-curable resin, a photopolymerization initiator, and the like.
  • the second composition can contain the same ionizing radiation-curable resin and photopolymerization initiator as the first composition. Therefore, detailed description is omitted.
  • the additives include silicone-based and fluorine-based additives (for example, leveling agents) that impart leveling, surface slip properties, high water contact angles, and the like.
  • the second hard coat layer 4 since the second hard coat layer 4 is required to have abrasion resistance, the second hard coat layer 4 contains an additive such as a fluorine-based additive (straight chain type) in order to impart a surface slip property, a high water contact angle, and the like. Is preferably performed.
  • the amount of these additives is not particularly limited, but is preferably, for example, 0.1 to 1.5 parts by weight, preferably 0.2 to 1.2 parts by weight, per 100 parts by weight of the second composition. Parts by weight, more preferably 0.3 to 1 part by weight.
  • the thickness of the second hard coat layer 4 is preferably 1 to 30 ⁇ m, more preferably 2 to 25 ⁇ m, and particularly preferably 3 to 15 ⁇ m. This is because if the thickness is less than 1 ⁇ m, the surface hardness of the cover film becomes insufficient. On the other hand, as the thickness of the second hard coat layer 4 is larger, the abrasion resistance performance is improved. However, if it is too large, the cover film may be curled due to shrinkage during production.
  • the second hard coat layer 4 is preferably 2H to 6H lower than that of the first hard coat layer in a surface pencil hardness test defined by JIS 5600-5-4 (1999). Thereby, as described later, the scratch resistance performance can be improved.
  • the method for manufacturing the cover film according to the present embodiment is not particularly limited, but can be performed as follows, for example.
  • the base film 1 is fed from the feeding roll on which the base film 1 is wound. Then, the first composition is applied to one surface of the base film 1.
  • a coating method for example, a known method such as a roll coater, a reverse roll coater, a gravure coater, a knife coater, and a bar coater can be adopted.
  • the first composition is dried.
  • the method of drying is not particularly limited, and for example, a method of passing the base material film coated with the first composition through a dryer.
  • the drying temperature at this time is preferably, for example, 40 to 100 ° C.
  • the first composition is cured by photopolymerization.
  • ultraviolet rays are preferably used as an ionizing radiation source, and a light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc, and a xenon arc can be used.
  • a light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc, and a xenon arc can be used.
  • a light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc, and a xenon arc.
  • the substrate film 1 is unwound from the take-up roll, and the first composition is applied to the surface opposite to the surface on which the first hard coat layer 2 is laminated in the same manner as described above, and the same method is used. Then, the first hard coat layer 2 is formed and wound on a winding roll.
  • the first hard coat layer 2 can be formed simultaneously by simultaneously applying and curing the first composition on both surfaces of the base film 1.
  • the base film 1 is unwound from the take-up roll, and the adhesive layer composition is applied onto one of the first hard coat layers 2 and dried to form the adhesive layer 3.
  • the second composition is applied on the adhesive layer 3, dried, and then cured by photopolymerization to form the second hard coat layer 4.
  • the substrate film 1 is wound around a winding roll to complete a cover film.
  • the cover film according to the present embodiment the following effects can be obtained. (1) Since the surface pencil hardness of the first hard coat layer 2 is as high as 7H or more, the surface hardness of the cover film can be increased.
  • the surface pencil hardness of the second hard coat layer 4 is lower than that of the first hard coat layer 2 and is 2H to 6H, scratch resistance can be improved. In particular, as the thickness of the second hard coat layer 4 is larger, the scratch resistance performance is improved. Further, when an additive such as a fluorine-based additive that improves the sliding property is contained, the scratch resistance can be further improved.
  • the surface pencil hardness of the second hard coat layer 4 is lower than that of the first hard coat layer 2, the surface pencil hardness of the first hard coat layer 2 is 7H or more, so that the surface hardness of the cover film is ensured. be able to.
  • the adhesion between the first hard coat layer 2 and the second hard coat layer 4 is increased, and the second hard coat layer 4 is peeled off when a scratch resistance test described later is performed. Can be prevented. Therefore, the scratch resistance performance can be improved.
  • the first hard coat layer 2 is laminated on both sides of the base film 1, but this can reduce the curl of the cover film.
  • the first hard coat layer 2 is laminated only on one surface of the base film 1, curling may occur due to shrinkage during manufacturing, depending on the thickness of the first hard coat layer 2. Therefore, it is advantageous to laminate the first hard coat layer 2 on both sides of the base film 1 as in the present embodiment.
  • a cover film in which the first hard coat layer 2, the adhesive layer 3, and the second hard coat layer 4 are sequentially laminated only on one surface of the base film 1 may be used. it can.
  • Examples 1 to 4 have the layer configuration shown in FIG.
  • the first hard coat layer was laminated on both sides of the base film, and the adhesive layer and the second hard coat layer were not provided.
  • Base film 100 ⁇ m thick PET film
  • Adhesive layer Polyester resin with a thickness of 2 ⁇ m
  • Composition 1 Polyfunctional acrylate (organic-inorganic hybrid)
  • Composition 2 Bifunctional urethane acrylate
  • Composition 3 Fluorine additive (linear type)
  • Composition 4 Fluorine additive (branched type) -Composition 5: Fluorine additive (linear type) -containing polyfunctional acrylate (containing only organic composition)
  • Composition 6 1-hydroxy-cyclohexyl phenyl ketone
  • Scratch resistance evaluation test> A steel wool # 0000 was placed on the surfaces of the second hard coat layers of Examples 1 to 4 and the first hard coat layer of the comparative example so that a load of 1 kgf / cm 2 was applied. Reciprocated. After reciprocating 10,000 times, the occurrence of scratches was visually confirmed. The results are as follows.
  • Examples 1 to 4 Although the surface pencil hardness of the second hard coat layer is not large, the surface pencil hardness of the first hard coat layer that supports the second hard coat layer is high, so that the surface of the cover film as a whole is high.
  • the pencil hardness is 7H or more in each case, and high surface hardness is realized. Therefore, in Examples 1 to 4, it is expected to prevent the occurrence of scratches such as dents when an external force acts.
  • Examples 1 to 4 show higher abrasion resistance performance than the comparative example having only one hard coat layer.
  • the scratch resistance was further improved.

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

A cover film according to the present invention comprises: a transparent base film; a first hard coat layer laminated on at least one surface of the base film; an adhesive layer laminated on the first hard coat layer; and a second hard coat layer laminated on the adhesive layer, having a film thickness that is thinner than that of the first hard coat layer, and containing a fluorine-based additive, wherein the surface pencil hardness of the first hard coat layer is 7 H or more, and the surface pencil hardness of the second hard coat layer is 2 H to 6 H inclusive.

Description

カバーフィルムCover film
　本発明は、カバーフィルムに関する。 The present invention relates to a cover film.
　近年、スマートフォンなどのディスプレイの表面を保護する種々のカバーフィルムが提案されている。例えば、特許文献１には、基材フィルムと、その表面に形成されたハードコート層とを有するカバーフィルムが提案されている。 In recent years, various cover films for protecting the surface of displays such as smartphones have been proposed. For example, Patent Document 1 proposes a cover film having a base film and a hard coat layer formed on the surface of the base film.
特開２０１５－７７３２号公報JP-A-2015-7732
　一般的に、ハードコート層は、外力によって傷や圧痕がつかないように高硬度であることが要求されている。これに加え、近年は、擦り傷などが生じないような耐擦傷性も要求されている。しかしながら、このような耐擦傷性は、単にハードコート層の硬度を高めるだけでは対応できなかった。本発明は、上記問題を解決するためになされたものであり、高硬度でありながら、耐擦傷性も向上することができる、ディスプレイ用のカバーフィルムを提供することを目的とする。 Generally, the hard coat layer is required to have high hardness so that scratches and dents are not caused by external force. In addition, in recent years, abrasion resistance that does not cause abrasion is required. However, such abrasion resistance cannot be dealt with simply by increasing the hardness of the hard coat layer. The present invention has been made to solve the above problems, and has as its object to provide a cover film for a display, which has high hardness and can also improve scratch resistance.
項１．透明の基材フィルムと、
　前記基材フィルムの少なくとも一方の面に積層された第１ハードコート層と、
　前記第１ハードコート層上に積層される接着層と、
　前記接着層上に積層され、前記第１ハードコート層よりも膜厚が小さく、フッ素系添加剤が含有される第２ハードコート層と、
を備え、
　前記第１ハードコート層の表面鉛筆硬度は、７Ｈ以上であり、
　前記第２ハードコート層の表面鉛筆硬度は、２Ｈ以上６Ｈ以下である、カバーフィルム。 Item 1. A transparent base film,
A first hard coat layer laminated on at least one surface of the base film,
An adhesive layer laminated on the first hard coat layer;
A second hard coat layer laminated on the adhesive layer, having a smaller film thickness than the first hard coat layer, and containing a fluorine-based additive;
With
The surface pencil hardness of the first hard coat layer is 7H or more,
The cover film, wherein the surface pencil hardness of the second hard coat layer is 2H or more and 6H or less.
項２．前記第１ハードコート層は、前記基材フィルムの両面に積層されており、
　一方の前記第１ハードコート層に、前記接着層及び前記第２ハードコート層がこの順で積層されている、項１に記載のカバーフィルム。 Item 2. The first hard coat layer is laminated on both sides of the base film,
Item 2. The cover film according to item 1, wherein the adhesive layer and the second hard coat layer are laminated on one of the first hard coat layers in this order.
項３．前記第１ハードコート層の膜厚は、５～５０μｍである、項１または２に記載のカバーフィルム。 Item 3. Item 3. The cover film according to item 1 or 2, wherein the first hard coat layer has a thickness of 5 to 50 μm.
項４．前記第２ハードコート層の膜厚は、１～３０μｍである、項１から３のいずれかに記載のカバーフィルム。 Item 4. Item 4. The cover film according to any one of Items 1 to 3, wherein the thickness of the second hard coat layer is 1 to 30 μm.
項５．前記第１ハードコート層は、分岐型のフッ素系添加剤を含有する、項１から４のいずれかに記載のカバーフィルム。 Item 5. Item 5. The cover film according to any one of Items 1 to 4, wherein the first hard coat layer contains a branched fluorine-based additive.
　本発明に係るカバーフィルムによれば、高硬度でありながら、耐擦傷性も向上することができる。 According to the cover film of the present invention, the scratch resistance can be improved while having high hardness.
本発明の一実施形態に係るカバーフィルムの断面図である。It is sectional drawing of the cover film which concerns on one Embodiment of this invention. 本発明の他の実施形態に係るカバーフィルムの断面図である。It is sectional drawing of the cover film which concerns on other embodiment of this invention.
　以下、本発明に係るカバーフィルムの一実施形態について、図面を参照しつつ説明する。図１は本発明の一実施形態に係るカバーフィルムの断面図である。図１に示すように、このカバーフィルムは、透明の基材フィルム１と、この基材フィルム１の両面に積層される第１ハードコート層２と、一方の第１ハードコート層２に積層される接着層３と、この接着層３に積層される第２ハードコート層４と、を備えている。以下、各部材について、詳細に説明する。 Hereinafter, an embodiment of a cover film according to the present invention will be described with reference to the drawings. FIG. 1 is a sectional view of a cover film according to an embodiment of the present invention. As shown in FIG. 1, this cover film is laminated on a transparent substrate film 1, a first hard coat layer 2 laminated on both sides of the substrate film 1, and one first hard coat layer 2. And a second hard coat layer 4 laminated on the adhesive layer 3. Hereinafter, each member will be described in detail.
　＜１．基材フィルム＞
　本実施形態に係る基材フィルム１は、透明の種々の材料で形成することができ、例えば、セルロースアシレート、シクロオレフィンポリマー、ポリカーボネート、アクリレート系ポリマー、ポリエステル、ポリイミドなどで形成することができる。また、この基材フィルム１には、必要に応じて種々の添加剤を添加することができる。例えば、可塑剤、帯電防止剤、紫外線吸収剤等の各種添加剤が添加されていてもよい。 <1. Base Film>
The substrate film 1 according to the present embodiment can be formed of various transparent materials, and can be formed of, for example, cellulose acylate, cycloolefin polymer, polycarbonate, acrylate polymer, polyester, polyimide, and the like. Various additives can be added to the base film 1 as needed. For example, various additives such as a plasticizer, an antistatic agent, and an ultraviolet absorber may be added.
　基材フィルム１の厚みは、例えば、２５μｍ以上３００μｍ以下であることが好ましく、５０μｍ以上２００μｍ以下であることがより好ましく、７５μｍ以上１２５μｍ以下であることがさらに好ましい。厚さが２５μｍ未満であると、第２ハードコート層４の表面において十分な表面硬度が得られず、３００μｍより大きいと、カバーフィルムの生産性が低下する。 厚 み The thickness of the base film 1 is, for example, preferably 25 μm or more and 300 μm or less, more preferably 50 μm or more and 200 μm or less, and even more preferably 75 μm or more and 125 μm or less. When the thickness is less than 25 μm, sufficient surface hardness cannot be obtained on the surface of the second hard coat layer 4, and when the thickness is more than 300 μm, the productivity of the cover film decreases.
　＜２．第１ハードコート層＞
　次に、第１ハードコート層２について説明する。第１ハードコート層２は、電離放射線硬化型樹脂、光重合開始剤などを含有する第１ハードコート層形成用樹脂組成物（以下、単に第１組成物という）を硬化させたものである。また、この組成物には、必要に応じて、後述する添加剤を配合することもできる。 <2. First hard coat layer>
Next, the first hard coat layer 2 will be described. The first hard coat layer 2 is obtained by curing a first hard coat layer forming resin composition (hereinafter, simply referred to as a first composition) containing an ionizing radiation-curable resin, a photopolymerization initiator, and the like. Further, additives described later can be added to this composition as needed.
　＜２－１．電離放射線硬化型樹脂＞
　電離放射線硬化型樹脂とは、電離放射線（紫外線または電子線）により高分子化または架橋反応するラジカル重合性を有する化合物を含み、例えば、構造単位中にエチレン性の不飽和結合を少なくとも１個以上含む化合物、またはこれらの混合物とすることができる。 <2-1. Ionizing radiation curable resin>
The ionizing radiation-curable resin includes a compound having a radical polymerizability that is polymerized or cross-linked by ionizing radiation (ultraviolet rays or electron beams). For example, at least one ethylenically unsaturated bond is contained in a structural unit. Or a mixture thereof.
　不飽和結合を１個含む単官能の化合物としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、グリシジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレートなどを挙げることができる。 Examples of the monofunctional compound containing one unsaturated bond include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, n-butyl (meth) acrylate, glycidyl (meth) acrylate, and cyclohexyl ( (Meth) acrylate and the like.
　また、不飽和結合を２個含む二官能の化合物としては、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ノナンジオールジ（メタ）アクリレート、エトキシ化ヘキサンジオールジ（メタ）アクリレート、プロポキシ化ヘキサンジオールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エトキシ化ネオペンチルグリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレートなどのジ（メタ）アクリレート等を挙げることができる。 Examples of the bifunctional compound containing two unsaturated bonds include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and nonane. Diol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, tripropylene Rikoruji (meth) acrylate and di (meth) acrylate, such as hydroxypivalic acid neopentyl glycol di (meth) acrylate.
　また、不飽和結合を３個以上含む多官能化合物としては、例えば、トリメチロールプロパントリ（メタ）アクリレート、エトキシ化トリメチロールプロパントリ（メタ）アクリレート、プロポキシ化トリメチロールプロパントリ（メタ）アクリレート、トリス２－ヒドロキシエチルイソシアヌレートトリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート等のトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート等の３官能の（メタ）アクリレート化合物や、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジトリメチロールプロパンペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジトリメチロールプロパンヘキサ（メタ）アクリレート等の３官能以上の多官能（メタ）アクリレート化合物や、これら（メタ）アクリレートの一部をアルキル基やε－カプロラクトンで置換した多官能（メタ）アクリレート化合物等の（メタ）アクリレート化合物を挙げることができる。 Examples of the polyfunctional compound containing three or more unsaturated bonds include, for example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, tris Tri (meth) acrylates such as 2-hydroxyethyl isocyanurate tri (meth) acrylate and glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate Trifunctional (meth) acrylate compounds such as acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol Trifunctional or higher polyfunctional (e.g., tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropanepenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropanehexa (meth) acrylate) Examples thereof include (meth) acrylate compounds and (meth) acrylate compounds such as polyfunctional (meth) acrylate compounds in which a part of the (meth) acrylate is substituted with an alkyl group or ε-caprolactone.
　その他、上記（メタ）アクリレート化合物に、ウレタン系樹脂を混合することもできる。ウレタン系樹脂としては、例えば、ウレタン（メタ）アクリレート系樹脂を用いることができる。具体的には、ウレタン（メタ）アクリレート化合物としては、ペンタエリスリトールトリアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー、ジペンタエリスリトールペンタアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー、ペンタエリスリトールトリアクリレートトルエンジイソシアネートウレタンプレポリマー、ジペンタエリスリトールペンタアクリレート、トルエンジイソシアネートウレタンプレポリマー、ペンタエリスリトールトリアクリレートイソホロンジイソシアネートウレタンプレポリマー、ジペンタエリスリトールペンタアクリレートイソホロンジイソシアネートウレタンプレポリマーなどを用いることができる。 In addition, a urethane-based resin can be mixed with the (meth) acrylate compound. As the urethane resin, for example, a urethane (meth) acrylate resin can be used. Specifically, as the urethane (meth) acrylate compound, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol Pentaacrylate, toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate isophorone diisocyanate urethane prepolymer, and the like can be used.
　ウレタン系樹脂の分子量は、１０００～１００００が好ましく、２０００～５０００がさらに好ましい。なお、本明細書で使用する分子量との文言は、標準ポリマーとしてポリスチレンを用い、ＧＰＣ法により測定した重量平均分子量を意味する。 The molecular weight of the urethane resin is preferably from 1,000 to 10,000, more preferably from 2,000 to 5,000. The term “molecular weight” used in the present specification means a weight average molecular weight measured by GPC using polystyrene as a standard polymer.
　＜２－２．光重合開始剤＞
　重合開始剤としては、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン等のベンジルメチルケタール類、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン等のα－ヒドロキシケトン類、２－メチル－１［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタノン－１等のα－アミノケトン類、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルフォスフィンオキサイド等のビスアシルフォスフィンオキサイド類、２，２'－ビス（ｏ－クロロフェニル）－４，４'，５，５'－テトラフェニル－１，１'－ビイミダゾール、ビス（２，４，５－トリフェニル）イミダゾール等のビスイミダゾール類、Ｎ－フェニルグリシン等のＮ－アリールグリシン類、４，４'－ジアジドカルコン等の有機アジド類、３，３'，４，４'－テトラ（ｔｅｒｔ－ブチルペルオキシカルボキシル）ベンゾフェノン等の有機過酸化物類をはじめ、Ｊ．Ｐｈｏｔｏｃｈｅｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，２，２８３（１９８７）．に記載される化合物を挙げることができる。 <2-2. Photopolymerization initiator>
Examples of the polymerization initiator include benzyl methyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropane-1 Α-hydroxy ketones such as 2-one, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Α-aminoketones such as phenyl) butanone-1, bisacylphosphine oxides such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and 2,2′-bis (o -Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,1'-biimidazole, bis (2,4,5-trif Nyl) Bisimidazoles such as imidazole, N-arylglycines such as N-phenylglycine, organic azides such as 4,4'-diazidochalcone, 3,3 ', 4,4'-tetra (tert-butyl) Organic peroxides such as peroxycarboxyl) benzophenone; Photochem. Sci. Technol. , 2,283 (1987). Can be mentioned.
　具体的には、鉄アレーン錯体、トリハロゲノメチル置換Ｓ－トリアジン、スルフォニウム塩、ジアゾニウム塩、フォスフォニウム塩、セレノニウム塩、アルソニウム塩、ヨードニウム塩等が挙げられる。また、ヨードニウム塩としては、Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，１０，１３０７（１９７７）．に記載の化合物、例えば、ジフェニルヨードニウム、ジトリルヨードニウム、フェニル（ｐ－アニシル）ヨードニウム、ビス（ｍ－ニトロフェニル）ヨードニウム、ビス（ｐ－ｔｅｒｔ－ブチルフェニル）ヨードニウム、ビス（p －クロロフェニル）ヨードニウムなどのヨードニウムのクロリド、ブロミド、あるいはホウフッ化塩、ヘキサフルオロフォスフェート塩、ヘキサフルオロアルセネート塩、芳香族スルホン酸塩等や、ジフェニルフェナシルスルホニウム（ｎ－ブチル）トリフェニルボレート等のスルホニウム有機ホウ素錯体類を挙げることができる。 Specifically, iron arene complexes, trihalogenomethyl-substituted S-triazines, sulfonium salts, diazonium salts, phosphonium salts, selenonium salts, arsonium salts, iodonium salts and the like can be mentioned. As iodonium salts, Macromolecules, 10, 1307 (1977). And the like, for example, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl) iodonium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p ド -chlorophenyl) iodonium and the like Iodonium chloride, bromide, or borofluoride salt, hexafluorophosphate salt, hexafluoroarsenate salt, aromatic sulfonate salt, or sulfonium organic boron complex such as diphenylphenacylsulfonium (n-butyl) triphenylborate And the like.
　＜２－３．添加剤＞
　第１組成物には、必要に応じて添加剤を配合することができる。例えば、レベリング、表面スリップ性、高水接触角性等を付与するシリコーン系、フッ素系の添加剤（例えば、レベリング剤）を挙げることができる。特に、第１ハードコート層２は、接着層３を積層するために、表面のレベリング性が求められるため、フッ素系添加物（分岐型）のような添加剤が含有されることが好ましい。これらの添加剤の配合量は、特には限定されないが、例えば、第１組成物１００重量部に対し、０．１～１．５重量部であることが好ましく、０．２～１．２重量部がより好ましく、０．３～１重量部がさらに好ましい。 <2-3. Additives>
An additive can be added to the first composition as needed. For example, a silicone-based or fluorine-based additive (for example, a leveling agent) that imparts leveling, surface slip properties, high water contact angle, and the like can be given. In particular, since the first hard coat layer 2 is required to have a surface leveling property in order to laminate the adhesive layer 3, it is preferable that the first hard coat layer 2 contains an additive such as a fluorine-based additive (branched type). The amount of these additives is not particularly limited, but is, for example, preferably 0.1 to 1.5 parts by weight, and more preferably 0.2 to 1.2 parts by weight based on 100 parts by weight of the first composition. Parts by weight, more preferably 0.3 to 1 part by weight.
　また、後述するように、第１ハードコート層２は、高い表面鉛筆硬度が求められるため、例えば、シリカ微粒子を混合することができる。シリカ微粒子としては、第１ハードコート層２の硬度を向上するものであれば特に制限されるものではないが、一次粒径５～１００ｎｍのシリカ微粒子を用いることが好ましく、一次粒径が１０～８０ｎｍのシリカ微粒子がさらに好ましい。また、シリカ微粒子の配合量は、特には限定されないが、例えば、第１組成物１００重量部に対し、２０～５０重量部であることが好ましく、３０～４０重量部がさらに好ましい。これは、２０重量部未満では鉛筆硬度の向上が見られにくい一方、５０重両部よりも多く配合すると耐摺動性能が低下するおそれがあることによる。 Further, as described later, since the first hard coat layer 2 is required to have a high surface pencil hardness, for example, silica fine particles can be mixed. The silica fine particles are not particularly limited as long as they improve the hardness of the first hard coat layer 2, but it is preferable to use silica fine particles having a primary particle size of 5 to 100 nm, and a primary particle size of 10 to 100 nm. 80 nm silica fine particles are more preferred. The amount of the silica fine particles is not particularly limited, but is, for example, preferably 20 to 50 parts by weight, more preferably 30 to 40 parts by weight, per 100 parts by weight of the first composition. This is because when less than 20 parts by weight, it is difficult to improve the pencil hardness, while when more than 50 parts by weight, the sliding resistance may be reduced.
　＜２－４．第１ハードコート層の物性＞
　第１ハードコート層２の厚みは、５～５０μｍであることが好ましく、１０～４５μｍであることがさらに好ましく、２０～４０μｍであることが特に好ましい。これは、５μｍ未満であると、カバーフィルムの表面硬度が不十分になるからである。一方、５０μｍより大きいとカバーフィルムの硬化収縮が大きくなり、製造時の収縮によりカバーフィルムがカールするおそれがある点で好ましくない。 <2-4. Physical Properties of First Hard Coat Layer>
The thickness of the first hard coat layer 2 is preferably 5 to 50 μm, more preferably 10 to 45 μm, and particularly preferably 20 to 40 μm. This is because if the thickness is less than 5 μm, the surface hardness of the cover film becomes insufficient. On the other hand, when the thickness is larger than 50 μm, the curing shrinkage of the cover film is increased, and the cover film is unfavorably curled due to shrinkage at the time of production.
　また、第１ハードコート層２は、ＪＩＳ５６００－５－４（１９９９）で規定する表面鉛筆硬度試験で、７Ｈ以上であることが好ましく、８Ｈ以上であることがさらに好ましい。これにより、後述するように、第１ハードコート層２上に積層される第２ハードコート層４の表面硬度を向上することができる。 The first hard coat layer 2 has a surface pencil hardness test defined by JIS 5600-5-4 (1999) of preferably 7H or more, more preferably 8H or more. Thereby, as described later, the surface hardness of the second hard coat layer 4 laminated on the first hard coat layer 2 can be improved.
　＜３．接着層＞
　接着層３は、第１及び第２ハードコート層１，２を接着できるものであれば、特には限定されないが、例えば、ポリウレタン系、ポリアクリル系、ポリエステル系、エポキシ系、ポリ酢酸ビニル系、塩ビ・酢ビ共重合物、セルロース系等の接着剤を適宜使用することができる。また、接着層３の厚みは、例えば、０．１～１０μｍとすることが好ましく、０．５～７μｍとすることがより好ましく、１～５μｍがさらに好ましい。 <3. Adhesive layer>
The adhesive layer 3 is not particularly limited as long as the adhesive layer 3 can bond the first and second hard coat layers 1 and 2, and examples thereof include polyurethane, polyacryl, polyester, epoxy, and polyvinyl acetate. An adhesive such as a polyvinyl chloride / vinyl acetate copolymer or a cellulose-based adhesive can be appropriately used. Further, the thickness of the adhesive layer 3 is preferably, for example, 0.1 to 10 μm, more preferably 0.5 to 7 μm, and still more preferably 1 to 5 μm.
　＜４．第２ハードコート層＞
　＜４－１．第２ハードコート層の組成＞
　次に、第２ハードコート層４について説明する。第２ハードコート層４は、電離放射線硬化型樹脂、光重合開始剤などを含有する第２ハードコート層形成用樹脂組成物（以下、単に第２組成物という）を硬化させたものである。第２組成物は、第１組成物と同様の電離放射線硬化型樹脂、光重合開始剤を含有することができる。したがって、詳細な説明は省略する。 <4. Second hard coat layer>
<4-1. Composition of Second Hard Coat Layer>
Next, the second hard coat layer 4 will be described. The second hard coat layer 4 is obtained by curing a second hard coat layer forming resin composition (hereinafter, simply referred to as a second composition) containing an ionizing radiation-curable resin, a photopolymerization initiator, and the like. The second composition can contain the same ionizing radiation-curable resin and photopolymerization initiator as the first composition. Therefore, detailed description is omitted.
　添加物については、例えば、レベリング、表面スリップ性、高水接触角性等を付与するシリコーン系、フッ素系の添加剤（例えば、レベリング剤）を挙げることができる。特に、第２ハードコート層４は、耐擦傷性が求められるため、表面スリップ性、高水接触角性等を付与するために、フッ素系添加物（直鎖型）のような添加剤が含有されることが好ましい。これらの添加剤の配合量は、特には限定されないが、例えば、第２組成物１００重量部に対し、０．１～１．５重量部とすることが好ましく、０．２～１．２重量部がより好ましく、０．３～１重量部がさらに好ましい。また、光重合の際に、紫外線を利用する場合は、上述した添加剤の空気界面へのブリードによって、酸素による樹脂の硬化阻害を低下させることができる。したがって、低照射強度条件下においても有効な硬化度合を得ることができる。 Examples of the additives include silicone-based and fluorine-based additives (for example, leveling agents) that impart leveling, surface slip properties, high water contact angles, and the like. In particular, since the second hard coat layer 4 is required to have abrasion resistance, the second hard coat layer 4 contains an additive such as a fluorine-based additive (straight chain type) in order to impart a surface slip property, a high water contact angle, and the like. Is preferably performed. The amount of these additives is not particularly limited, but is preferably, for example, 0.1 to 1.5 parts by weight, preferably 0.2 to 1.2 parts by weight, per 100 parts by weight of the second composition. Parts by weight, more preferably 0.3 to 1 part by weight. In the case where ultraviolet rays are used during photopolymerization, the above-mentioned bleeding of the additive to the air interface can reduce the curing inhibition of the resin due to oxygen. Therefore, an effective curing degree can be obtained even under low irradiation intensity conditions.
　＜４－２．第２ハードコート層の物性＞
　第２ハードコート層４の厚みは、１～３０μｍであることが好ましく、２～２５μｍであることがさらに好ましく、３～１５μｍであることが特に好ましい。これは、１μｍ未満であると、カバーフィルムの表面硬度が不十分になるからである。一方、第２ハードコート層４の厚みが大きいほど、耐擦傷性能は向上するが、大きすぎると、製造時の収縮によりカバーフィルムがカールするおそれがある。 <4-2. Physical Properties of Second Hard Coat Layer>
The thickness of the second hard coat layer 4 is preferably 1 to 30 μm, more preferably 2 to 25 μm, and particularly preferably 3 to 15 μm. This is because if the thickness is less than 1 μm, the surface hardness of the cover film becomes insufficient. On the other hand, as the thickness of the second hard coat layer 4 is larger, the abrasion resistance performance is improved. However, if it is too large, the cover film may be curled due to shrinkage during production.
　また、第２ハードコート層４は、ＪＩＳ５６００－５－４（１９９９）で規定する表面鉛筆硬度試験で、第１ハードコート層よりも低い２Ｈ～６Ｈであることが好ましい。これにより、後述するように、耐擦傷性能を向上することができる。 The second hard coat layer 4 is preferably 2H to 6H lower than that of the first hard coat layer in a surface pencil hardness test defined by JIS 5600-5-4 (1999). Thereby, as described later, the scratch resistance performance can be improved.
　＜５．カバーフィルムの製造方法＞
　本実施形態に係るカバーフィルムの製造方法は、特には限定されないが、例えば、次のように行うことができる。 <5. Manufacturing method of cover film>
The method for manufacturing the cover film according to the present embodiment is not particularly limited, but can be performed as follows, for example.
　まず、基材フィルム１を巻き取った繰り出しロールから基材フィルム１を繰り出す。そして、基材フィルム１の一方の面に第１組成物を塗布する。塗布方法としては、例えば、ロールコーター、リバースロールコーター、グラビアコーター、ナイフコーター、バーコーター等の公知の方法を採用することができる。次に、第１組成物を乾燥させる。乾燥の方法は、特には限定されないが例えば、第１組成物が塗布された基材フィルムを、乾燥器内を通過させる方法が挙げられる。このときの乾燥温度は、例えば、４０～１００℃であることが好ましい。その後、第１組成物を光重合により硬化させる。この硬化には、電離放射線源として紫外線を使用することが好ましく、高圧水銀灯、低圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアーク、キセノンアーク等の光源を利用することができる。こうして、第１組成物が硬化し、第１ハードコート層２が形成される。その後、この基材フィルム１を巻き取りロールに巻き取る。なお、上記組成物の塗布、乾燥、光重合は、次に説明する接着層及び第２ハードコート層においても同様の方法が適用できる。 (1) First, the base film 1 is fed from the feeding roll on which the base film 1 is wound. Then, the first composition is applied to one surface of the base film 1. As a coating method, for example, a known method such as a roll coater, a reverse roll coater, a gravure coater, a knife coater, and a bar coater can be adopted. Next, the first composition is dried. The method of drying is not particularly limited, and for example, a method of passing the base material film coated with the first composition through a dryer. The drying temperature at this time is preferably, for example, 40 to 100 ° C. Thereafter, the first composition is cured by photopolymerization. For this curing, ultraviolet rays are preferably used as an ionizing radiation source, and a light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc, and a xenon arc can be used. Thus, the first composition is cured, and the first hard coat layer 2 is formed. Thereafter, the base film 1 is wound around a winding roll. In addition, the same method can be applied to the adhesive layer and the second hard coat layer described below for application, drying, and photopolymerization of the composition.
　次に、この巻き取りロールから基材フィルム１を繰り出し、第１ハードコート層２が積層された面とは反対側の面に、上記と同様に第１組成物を塗布し、同様の方法で、第１ハードコート層２を形成し、巻き取りロールに巻き取る。なお、基材フィルム１の両面に対し、同時に第１組成物を塗布し、硬化させることで、第１ハードコート層２を同時に形成することもできる。 Next, the substrate film 1 is unwound from the take-up roll, and the first composition is applied to the surface opposite to the surface on which the first hard coat layer 2 is laminated in the same manner as described above, and the same method is used. Then, the first hard coat layer 2 is formed and wound on a winding roll. The first hard coat layer 2 can be formed simultaneously by simultaneously applying and curing the first composition on both surfaces of the base film 1.
　続いて、巻き取りロールから基材フィルム１を繰り出し、一方の第１ハードコート層２上に接着層用組成物を塗布し、乾燥することで接着層３を形成する。次に、接着層３上に第２組成物を塗布し、乾燥した後、光重合により硬化し、第２ハードコート層４を形成する。その後、この基材フィルム１を巻き取りロールに巻き取り、カバーフィルムが完成する。 Subsequently, the base film 1 is unwound from the take-up roll, and the adhesive layer composition is applied onto one of the first hard coat layers 2 and dried to form the adhesive layer 3. Next, the second composition is applied on the adhesive layer 3, dried, and then cured by photopolymerization to form the second hard coat layer 4. Thereafter, the substrate film 1 is wound around a winding roll to complete a cover film.
　＜６．特徴＞
　本実施形態に係るカバーフィルムによれば、以下の効果を得ることができる。
（１）第１ハードコート層２の表面鉛筆硬度が７Ｈ以上と高いため、カバーフィルムの表面硬度を高めることができる。 <6. Features>
According to the cover film according to the present embodiment, the following effects can be obtained.
(1) Since the surface pencil hardness of the first hard coat layer 2 is as high as 7H or more, the surface hardness of the cover film can be increased.
（２）第２ハードコート層４の表面鉛筆硬度を、第１ハードコート層２よりも低く、２Ｈ～６Ｈであるため、耐擦傷性を向上することができる。特に、第２ハードコート層４の膜厚が大きいほど、耐擦傷性能が向上する。また、フッ素系添加物のような摺動性を向上する添加物を含有させると、より耐擦傷性能を向上ることができる。なお、第２ハードコート層４の表面鉛筆硬度は第１ハードコート層２よりも低いが、第１ハードコート層２の表面鉛筆硬度は７Ｈ以上であるため、カバーフィルムとしての表面硬度を担保することができる。 (2) Since the surface pencil hardness of the second hard coat layer 4 is lower than that of the first hard coat layer 2 and is 2H to 6H, scratch resistance can be improved. In particular, as the thickness of the second hard coat layer 4 is larger, the scratch resistance performance is improved. Further, when an additive such as a fluorine-based additive that improves the sliding property is contained, the scratch resistance can be further improved. Although the surface pencil hardness of the second hard coat layer 4 is lower than that of the first hard coat layer 2, the surface pencil hardness of the first hard coat layer 2 is 7H or more, so that the surface hardness of the cover film is ensured. be able to.
（３）接着層３を設けることで、第１ハードコート層２と第２ハードコート層４との密着性が高まり、後述する耐擦傷性試験を行ったとき、第２ハードコート層４が剥がれるのを防止することができる。したがって、耐擦傷性能を向上することができる。 (3) By providing the adhesive layer 3, the adhesion between the first hard coat layer 2 and the second hard coat layer 4 is increased, and the second hard coat layer 4 is peeled off when a scratch resistance test described later is performed. Can be prevented. Therefore, the scratch resistance performance can be improved.
（４）本実施形態では、基材フィルム１の両面に第１ハードコート層２を積層しているが、これにより、カバーフィルムのカールを低減することができる。例えば、基材フィルム１の一方面にのみ、第１ハードコート層２を積層すると、第１ハードコート層２の膜厚にもよるが、製造時の収縮によりカールが生じるおそれがある。したがって、本実施形態のように第１ハードコート層２を基材フィルム１の両面に積層すると有利である。但し、図２に示すように、基材フィルム１の一方の面にのみ、第１ハードコート層２、接着層３、及び第２ハードコート層４を順次積層したものをカバーフィルムとすることもできる。 (4) In the present embodiment, the first hard coat layer 2 is laminated on both sides of the base film 1, but this can reduce the curl of the cover film. For example, if the first hard coat layer 2 is laminated only on one surface of the base film 1, curling may occur due to shrinkage during manufacturing, depending on the thickness of the first hard coat layer 2. Therefore, it is advantageous to laminate the first hard coat layer 2 on both sides of the base film 1 as in the present embodiment. However, as shown in FIG. 2, a cover film in which the first hard coat layer 2, the adhesive layer 3, and the second hard coat layer 4 are sequentially laminated only on one surface of the base film 1 may be used. it can.
　次に、本発明の実施例について説明する。但し、本発明は、以下の実施例に限定されない。 Next, examples of the present invention will be described. However, the present invention is not limited to the following embodiments.
　＜１．実施例及び比較例の作製＞
　以下では、実施例１～４及び比較例に係るカバーフィルムの作製について説明する。実施例１～４は、上記図１で示す層構成を有している。一方、比較例は、基材フィルムの両面に第１ハードコート層が積層され、接着層及び第２ハードコート層は設けられていない。 <1. Production of Examples and Comparative Examples>
Hereinafter, the production of the cover films according to Examples 1 to 4 and Comparative Example will be described. Examples 1 to 4 have the layer configuration shown in FIG. On the other hand, in the comparative example, the first hard coat layer was laminated on both sides of the base film, and the adhesive layer and the second hard coat layer were not provided.
(1) 基材フィルム：１００μｍ厚のＰＥＴフィルム
(2) 接着層：ポリエステル系樹脂を膜厚２μｍで成膜 (1) Base film: 100 μm thick PET film
(2) Adhesive layer: Polyester resin with a thickness of 2 μm
(3) 第１ハードコート層、第２ハードコート層の組成
Figure JPOXMLDOC01-appb-T000001
 (単位は重量部)
・組成１：多官能アクリレート(有機－無機ハイブリッド)
・組成２：２官能ウレタンアクリレート
・組成３：フッ素系添加剤（直鎖型）
・組成４：フッ素系添加剤（分岐型）
・組成５：フッ素系添加剤（直鎖型）含有多官能アクリレート（有機系の組成のみ含有）
・組成６：１－ヒドロキシ－シクロへキシルフェニルケトン (3) Composition of first hard coat layer and second hard coat layer
Figure JPOXMLDOC01-appb-T000001
 (Unit is parts by weight)
・ Composition 1: Polyfunctional acrylate (organic-inorganic hybrid)
・ Composition 2: Bifunctional urethane acrylate ・ Composition 3: Fluorine additive (linear type)
・ Composition 4: Fluorine additive (branched type)
-Composition 5: Fluorine additive (linear type) -containing polyfunctional acrylate (containing only organic composition)
Composition 6: 1-hydroxy-cyclohexyl phenyl ketone
(4) 第１ハードコート層、第２ハードコート層の膜厚(単位はμｍ)
Figure JPOXMLDOC01-appb-T000002
 (4) Film thickness of the first hard coat layer and the second hard coat layer (unit: μm)
Figure JPOXMLDOC01-appb-T000002
(5) 第１ハードコート層及び第２ハードコート層の表面鉛筆硬度
　実施例１～４及び比較例を構成する第１ハードコート層及び第２ハードコート層の表面鉛筆硬度は、以下の通りである。なお、表面鉛筆硬度は、ＪＩＳ５６００－５－４（１９９９）で規定する表面鉛筆硬度試験にて測定した。
Figure JPOXMLDOC01-appb-T000003
 (5) Surface Pencil Hardness of First Hard Coat Layer and Second Hard Coat Layer Surface pencil hardness of the first hard coat layer and the second hard coat layer constituting Examples 1 to 4 and Comparative Example are as follows. is there. The surface pencil hardness was measured by a surface pencil hardness test specified in JIS 5600-5-4 (1999).
Figure JPOXMLDOC01-appb-T000003
　＜２．表面鉛筆硬度試験＞
　上記実施例１～４及び比較例に対し、ＪＩＳ５６００－５－４（１９９９）で規定する表面鉛筆硬度試験を行った。実施例１～８に対しては、第２ハードコート層に試験を行った。一方、比較例に対しては、第１ハードコート層に試験を行った。結果は、以下の通りである。
Figure JPOXMLDOC01-appb-T000004
 <2. Surface pencil hardness test>
A surface pencil hardness test specified in JIS 5600-5-4 (1999) was performed on Examples 1 to 4 and Comparative Example. For Examples 1 to 8, a test was performed on the second hard coat layer. On the other hand, for the comparative example, a test was performed on the first hard coat layer. The results are as follows.
Figure JPOXMLDOC01-appb-T000004
　＜３．耐擦傷性評価試験＞
　実施例１～４の第２ハードコート層、及び比較例の第１ハードコート層の表面に１ｋｇｆ／ｃｍ2の荷重がかかるようにスチールウール＃００００を配置し、１４ｃｍ／ｓｅｃの速度で、７ｃｍ往復させた。そして、１００００往復させ、傷の発生を目視で確認した。結果は、以下の通りである。
Figure JPOXMLDOC01-appb-T000005
 <3. Scratch resistance evaluation test>
A steel wool # 0000 was placed on the surfaces of the second hard coat layers of Examples 1 to 4 and the first hard coat layer of the comparative example so that a load of 1 kgf / cm 2 was applied. Reciprocated. After reciprocating 10,000 times, the occurrence of scratches was visually confirmed. The results are as follows.
Figure JPOXMLDOC01-appb-T000005
　＜４．考察＞
　上記のように、実施例１～４では、第２ハードコート層の表面鉛筆硬度は大きくはないものの、これを支持する第１ハードコート層の表面鉛筆硬度が高いため、カバーフィルム全体としての表面鉛筆硬度は、いずれも７Ｈ以上となっており、高い表面硬度が実現されている。したがって、実施例１～４では、外力が作用したときの凹みなどの傷が生じるのを防止することが期待される。 <4. Discussion>
As described above, in Examples 1 to 4, although the surface pencil hardness of the second hard coat layer is not large, the surface pencil hardness of the first hard coat layer that supports the second hard coat layer is high, so that the surface of the cover film as a whole is high. The pencil hardness is 7H or more in each case, and high surface hardness is realized. Therefore, in Examples 1 to 4, it is expected to prevent the occurrence of scratches such as dents when an external force acts.
　一方、耐擦傷性試験において、実施例１～４は、ハードコート層が一層しかない比較例に比べ高い耐擦傷性能を示している。特に、実施例２～４のように第２ハードコート層の膜厚が大きくなると、耐擦傷性能がさらに高くなることが分かった。 On the other hand, in the abrasion resistance test, Examples 1 to 4 show higher abrasion resistance performance than the comparative example having only one hard coat layer. In particular, it was found that as the thickness of the second hard coat layer was increased as in Examples 2 to 4, the scratch resistance was further improved.
１　基材フィルム
２　第１ハードコート層
３　接着層
４　第２ハードコート層 Reference Signs List 1 base film 2 first hard coat layer 3 adhesive layer 4 second hard coat layer

Claims (5)

  1. 　透明の基材フィルムと、
    　前記基材フィルムの少なくとも一方の面に積層された第１ハードコート層と、
    　前記第１ハードコート層上に積層される接着層と、
    　前記接着層上に積層され、前記第１ハードコート層よりも膜厚が小さく、フッ素系添加剤が含有される第２ハードコート層と、
    を備え、
    　前記第１ハードコート層の表面鉛筆硬度は、７Ｈ以上であり、
    　前記第２ハードコート層の表面鉛筆硬度は、２Ｈ以上６Ｈ以下である、カバーフィルム。     A transparent base film,
    A first hard coat layer laminated on at least one surface of the base film,
    An adhesive layer laminated on the first hard coat layer;
    A second hard coat layer laminated on the adhesive layer, having a smaller film thickness than the first hard coat layer, and containing a fluorine-based additive;
    With
    The surface pencil hardness of the first hard coat layer is 7H or more,
    The cover film, wherein the surface pencil hardness of the second hard coat layer is 2H or more and 6H or less.
  2. 　前記第１ハードコート層は、前記基材フィルムの両面に積層されており、
    　一方の前記第１ハードコート層に、前記接着層及び前記第２ハードコート層がこの順で積層されている、請求項１に記載のカバーフィルム。     The first hard coat layer is laminated on both sides of the base film,
    The cover film according to claim 1, wherein the adhesive layer and the second hard coat layer are laminated on one of the first hard coat layers in this order.
  3. 　前記第１ハードコート層の膜厚は、５～５０μｍである、請求項１または２に記載のカバーフィルム。 The cover film according to claim 1, wherein the thickness of the first hard coat layer is 5 to 50 μm.
  4. 　前記第２ハードコート層の膜厚は、１～３０μｍである、請求項１から３のいずれかに記載のカバーフィルム。 4. The cover film according to claim 1, wherein the second hard coat layer has a thickness of 1 to 30 μm.
  5. 　前記第１ハードコート層は、分岐型のフッ素系添加剤を含有する、請求項１から４のいずれかに記載のカバーフィルム。 The cover film according to any one of claims 1 to 4, wherein the first hard coat layer contains a branched fluorine-based additive.
PCT/JP2019/037616 2018-09-27 2019-09-25 Cover film WO2020067165A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020506284A JP6733071B1 (en) 2018-09-27 2019-09-25 Cover film

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-182514 2018-09-27
JP2018182514 2018-09-27

Publications (1)

Publication Number Publication Date
WO2020067165A1 true WO2020067165A1 (en) 2020-04-02

Family

ID=69952863

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/037616 WO2020067165A1 (en) 2018-09-27 2019-09-25 Cover film

Country Status (2)

Country Link
JP (1) JP6733071B1 (en)
WO (1) WO2020067165A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114774019A (en) * 2022-04-24 2022-07-22 武汉华星光电半导体显示技术有限公司 Display screen cover plate and display device

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011031575A (en) * 2009-08-05 2011-02-17 Mitsubishi Rayon Co Ltd Laminate and method for manufacturing the same
JP2011140170A (en) * 2010-01-07 2011-07-21 Mitsubishi Rayon Co Ltd Method for manufacturing laminated body
WO2017014198A1 (en) * 2015-07-17 2017-01-26 大日本印刷株式会社 Laminate for optical members and image display device
WO2017098935A1 (en) * 2015-12-08 2017-06-15 リケンテクノス株式会社 Hard coat layered film
JP2017159506A (en) * 2016-03-08 2017-09-14 グンゼ株式会社 Surface protective film
JP2018047691A (en) * 2016-09-05 2018-03-29 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． Hard coating film and image display device including the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4075147B2 (en) * 1998-08-04 2008-04-16 凸版印刷株式会社 Hard coat film or sheet, and hard coat film or sheet with functional inorganic thin film
JP2013117584A (en) * 2011-12-01 2013-06-13 Keiwa Inc Hard coat film, transparent conductive laminate, and touch panel
JP2015106033A (en) * 2013-11-29 2015-06-08 凸版印刷株式会社 Optical film
JP7016602B2 (en) * 2015-07-17 2022-02-07 大日本印刷株式会社 Hard-coated film for touch panels and foldable image display device
US20170253706A1 (en) * 2016-03-04 2017-09-07 Dongwoo Fine-Chem Co., Ltd. Hard Coating Film

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011031575A (en) * 2009-08-05 2011-02-17 Mitsubishi Rayon Co Ltd Laminate and method for manufacturing the same
JP2011140170A (en) * 2010-01-07 2011-07-21 Mitsubishi Rayon Co Ltd Method for manufacturing laminated body
WO2017014198A1 (en) * 2015-07-17 2017-01-26 大日本印刷株式会社 Laminate for optical members and image display device
WO2017098935A1 (en) * 2015-12-08 2017-06-15 リケンテクノス株式会社 Hard coat layered film
JP2017159506A (en) * 2016-03-08 2017-09-14 グンゼ株式会社 Surface protective film
JP2018047691A (en) * 2016-09-05 2018-03-29 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． Hard coating film and image display device including the same

Also Published As

Publication number Publication date
JP6733071B1 (en) 2020-07-29
JPWO2020067165A1 (en) 2021-01-07

Similar Documents

Publication Publication Date Title
JP6462941B1 (en) Cover film
JP2014186210A (en) Hard coat film
JP5737573B2 (en) Release film and method for producing resin laminate
JP2014115502A (en) Optical film
JP6334035B1 (en) Cover film
WO2020067165A1 (en) Cover film
JP2015007732A (en) Hard coat film
JP6363769B1 (en) Cover film
WO2023068040A1 (en) Hard coat film and method for manufacturing same
JP2011115981A (en) Double-sided hard coat film
JP6844057B1 (en) Cover film and its manufacturing method
JP2015106033A (en) Optical film
JP6998730B2 (en) Cover film
JP2006070062A (en) Antistatic hard coat coating, antistatic hard coat film using the same and molding
JP6815550B1 (en) Cover film and its manufacturing method
JP2018035291A (en) Curable composition, surface layer film formation base material using the same, and method for producing surface layer film formation base material
JP2649051B2 (en) Transfer sheet manufacturing method
JP2006181791A (en) Transfer material and laminate
JP2002172743A (en) Surface protective film
JP5196757B2 (en) Hard coat film and molded body
KR20200115220A (en) Cover film
JP2014089406A (en) Optical film
JP2017193628A (en) Resin molding and method for producing the same

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2020506284

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19866377

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19866377

Country of ref document: EP

Kind code of ref document: A1