TW200823255A - Protective self-adhesive film, screen panel, and mobile electronic terminal - Google Patents

Abstract

The present invention provides a protective self-adhesive film, formed by a base material combined with a rigid hard coat film and an adhesive layer. The base material has an elasticity modulus of 3-7 Gpa and a thickness of 38-100 μm. The rigid hard coat film has a thickness of 5-25 μm and a surface hardness (pencil hardness) of over 3H. The adhesive layer has a thickness of 5-20 μm. The invented protective self-adhesive film has a total thickness of 60-150 μm. Furthermore, the adhesive layer has a storage elasticity modulus in 1 Hz dynamic viscoelastic spectrum at 80 DEG C of over 1.0x10Λ5Pa.

Description

200823255 w IX. OBJECTS OF THE INVENTION · Technical Field of the Invention The present invention relates to a protective adhesive film for protecting a screen panel disposed on a surface of a display device such as a liquid crystal panel or an EL display, and a film having an adhesive film. A screen panel and a portable electronic terminal having the screen panel. [Prior Art] With the development of miniaturization of portable electronic terminal devices, thinning of image_display devices (hereinafter referred to as display devices) is progressing. In order to prevent breakage of a display device such as a liquid crystal, a screen panel for protection (hereinafter referred to as a panel) is provided. In order to achieve a reduction in thickness, it is effective to reduce the thickness of the panel and to reduce the gap between the display device and the panel. However, in the case of conventional resin panels such as acrylics and polycarbonates, the rigidity of the panel is insufficient, so that the display device may be opened when the panel portion is pressed with a finger. 'The display is poor, or the long-term durability test such as wet heat conditions. The time panel will be partially attached to the image display panel. Therefore, a high-rigidity screen panel that replaces the conventional resin-made screen panel has been sought, for example, a glass panel has been used. However, glass panels require safety measures when they are broken. Therefore, it has been studied to attach a protective adhesive film having a function of preventing scattering on the surface of the panel. As a protective adhesive film, Patent Document 1 discloses a polarizing plate for a liquid crystal display or a hard coat film for protection of various displays. The disclosed hard coat film used a 188 micron PET film for the underlayer film to exhibit a surface stray hardness of 4H, but since the film thickness is thick, 5 200823255 is not suitable for the purpose of thinning. In addition, when the same hard coating agent is placed on the underlying film of the soil, if the structure is not adhered to the w layer of the thin cloth, the higher surface pencil hardness is required, but if the w is increased on the panel, the barrier is In the case of the donor layer, the adhesive layer will (4), and the hardness of the adhesive pen is greatly reduced.乍 is the surface lead of the panel. In addition, when the type of the soil coating 1 of the image display device is formed, the requirement for thinning is also high. As a kind of surface protection sheet, it is a type of surface protection sheet which is scratch-resistant and chemical-resistant. It is used for surface protection adhesive sheets such as photo papers (see patent documents) ^ ) . However, the surface of the adhesive sheet is insufficient. In order to be applied to an image display device, further improvement is required. Moreover, since the protective adhesive sheet is used as the outermost layer of the image display device, it is required to have excellent peeling resistance, and the use of softness in order to ensure the adhesive force is not the case. Causing foaming in a high humidity environment. Patent Document 1 - Japanese Patent Laid-Open No. 2-5_32〇522

Patent Document 2: Japanese Patent Laid-Open No. 2, No. 9 641 【 SUMMARY OF THE INVENTION The problem to be solved by the present invention is to provide a protective adhesive film which is formed to have a thin thickness even when laminated with an adhesive or the like by a glass plate or the like. The panel can also maintain a high surface hardness, and it is difficult to produce a foamed adhesive film in a high-temperature and high-humidity environment, and provides a screen panel which has both thinness, suitable elasticity, high surface hardness and excellent visual properties. And providing a portable electronic terminal that is difficult to cause damage on the surface of the panel and is excellent in visual visibility. In the present invention, even by a hard hard coating film (with a specific thickness group 6 200823255 « special elastic pull number of substrate and hard hard The coating layer is provided with a specific thickness, and the protective adhesive film of the layer is adhered to the adhering object through the adhesive layer. When a pressure is locally applied by impact or the like to protect the surface of the adhesive film, even a thin thickness, It is also possible to suitably alleviate the depression of the film which is swelled by the adhesive layer, and it is possible to satisfactorily exhibit the characteristics of the hard coat film without the adhesive layer. The viscoelasticity of the adhesive layer can maintain the above-mentioned excellent surface hardness, and at the same time, can achieve a suitable adhesive force, and can suppress the generation of bubbles when adhered to the attached object. That is, the present invention provides a protective adhesive film. The hard coating film formed on the film substrate having a hard coat layer is provided with an adhesive layer; and the film substrate has a modulus of elasticity of 3 to 7 GPa and a thickness of 38 to 1 , the thickness of the hard coat layer is 5 to 25 μm. The pencil hardness of the surface of the hard coat layer of the hard coat film is 3 Å or more, and the thickness of the adhesive layer is 5 〜 2 〇 μιη, and the total thickness is 60 〜1 5 Ομπι 〇 When the protective adhesive film of the present invention is used for the protective use of a thin glazed glass panel such as a portable electronic terminal, it can be suitably used because of its high surface pencil hardness, or can be suitably used for protection of various displays. In addition, when the object to be adhered is ruptured by glass or the like, it can be effectively used as a scattering preventing film that prevents scattering when the adhering object is broken. [Embodiment] [Film substrate] In the present invention, a film substrate having an elastic modulus of 7 200823255 and a light transmittance of 85% or more is used in the present invention. As a protective adhesive film for protecting the surface of a dry body, etc., the appearance is problematic. In view of the problem of peeling due to fishing damage at the edge portion, it is preferably at least 15 μm μm or less. Therefore, the base film must be a thin substrate, and at least it must be laminated from other layers. 1〇〇_以下. At this time, if the elastic modulus is less than 3 GPa, the film substrate is likely to be deformed when the protective adhesive film is formed, and the surface hardness cannot be suppressed when the protective adhesive film is formed. When the thickness is 7 (10) or more, the film substrate is too hard, and the curved surface cannot be followed when the adhesive film is adhered. Further, when the thickness is less than 38, the film substrate is likely to be deformed even in the elastic modulus range. The setting of the adhesive layer becomes impossible to suppress the reduction in surface hardness. Further, the light transmittance is preferably 85% or more, more preferably _ or more. Examples of the film substrate used in the present invention include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene film, and polypropylene. Membrane, cellophane, cellulose diacetate film, cellulose acetate film, cellulose acetate butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl acetate Copolymer film, polystyrene film, polysulphonate film, polymethylpentene film, polysulfone film, polyether ether ketone film to ether sulfone film, polyether sulfimine film, polyimine film, fluorine A resin film, a nylon film, an acrylic resin film, or the like. In addition, for the purpose of improving the adhesion to the hard coat layer and the adhesive layer, surface roughening treatment such as sand blasting or solvent treatment, or smear treatment, chromic acid treatment, flame treatment, hot air treatment, and ozone are carried out. · Surface treatment such as surface oxidation treatment such as ultraviolet irradiation treatment. 8 200823255 Antistatic agents can be added as other compounding materials to impart antistatic properties. Nonionics include: & oxyethylene ether, polyoxyethylene oxime, polyoxyethylene (tetra)amine, polyoxyethylene (tetra) decylamine, fatty acid polyethylene glycol vinegar, fatty acid sorbitan _, polyoxyethylene fatty acid sorbitan vinegar, fatty acid glycerides, alkyl polyethylene imine and the like. The cation group may, for example, be an alkylamine salt, an alkyl quaternary ammonium salt or an alkyl imidazoline derivative. Further, an acrylate compound having an ethylene oxide in the skeleton or the like can also be used. As the conductive polymer, polyaniline, polypyrrole, polythiophene, poly-3,4-extended ethyldioxythiophene, and the like can be used. As the metal oxide, cerium-doped tin oxide (AT0), tin-doped indium oxide (IT〇), Ilu 6-type zinc oxide, emulsified yttrium or the like can be used. In addition to this, an ion conductive antistatic agent in which metal ions such as a clock ion are mixed may be used. [Hard Coat Layer] The hard coat layer used in the present invention may have a hardness of 3 Å or more when laminated with the above-mentioned film substrate, and a hard coat layer formed of a cured product of various hard coat agents may be used. As the hard coating agent, an active energy ray-curable resin composition can be suitably used. Among them, a polymer (A) having a (meth)acryl fluorenyl group and three or more molecules in one molecule are particularly preferable ( A reactive energy ray-curable resin composition of a polyfunctional (fluorenyl) acrylate (B) having a methyl methacrylate group, the side chain of the polymer (A) having a (fluorenyl) propylene group being reactive A composition obtained by reacting a functional group (indenyl) acrylate-based polymer (al) with an α,β-unsaturated compound (a2) having a functional group reactive with the above reactive functional group, because of the resulting hardening Matter 9 200823255 It is difficult to cause warpage, and it is difficult to lower the surface hardness when the adhesive layer is provided on the hard coat film in which the cured product of the composition is a hard coat layer. Here, 'in the present invention, sulfhydryl propylene vinegar vinegar means one or both of methacrylic acid vinegar and acrylic vinegar, "(indenyl) acrylonitrile" and "(meth)acrylic acid" The same is true.

The reactive functional group of the (meth) acrylate-based polya- (a 1 ) having a reactive functional group in the side chain is preferably a hydroxyl group, a substituent or an epoxy group. The functional group of the α, unsaturated compound (U) which reacts with the reactive functional groups is preferably an isocyanate group, a carboxyl group, a halogenated fluorenyl group, a hydroxyl group or an epoxy group. Here, the (meth)acrylic acid-based polymer (al) having a reactive functional group in the side chain and the α,β-unsaturated compound (a2) having a functional group reactive with the above reactive functional group The method for producing the (meth)acrylonitrile-based polymer (A) after the reaction is not particularly limited, and it can be produced by a conventionally known method, and examples thereof include the following production methods (1). a (meth) acrylate polymer or copolymer having a reactive functional group as a fluorene (meth) acrylate polymer, (.methyl) propylene decyl ethyl isocyanate, (methyl meth) a method for producing a (meth)propanyl group as a ?,anthracene-hydrogen compound or the like as a ?,anthracene-unsaturated compound "2) 2: a group-partially or wholly-reacted reaction (2) using a side chain e-e ^ ^ "Reactive g-energy group (meth) propylene vinegar 200823255 polymer or copolymer as the above (meth) acrylate polymer (al), containing hydroxyl group and (meth) propylene hydride Acrylic acid, or having an epoxy group and a (meth) acrylonitrile group The acrylate is a method in which an α,β-unsaturated compound (a2) is reacted with a part or all of the carboxyl group to introduce a (meth)acryloyl group. The production method (3) employs a side chain having a reactive functional group epoxy group. (Meth)acrylic vinegar-based polymer or copolymer as the above (meth)acrylate-based polymer (al), (meth)acrylic acid or acrylic acrylate having a carboxyl group and an acrylonitrile group as (χ, β-not A method in which a saturated compound (a2) is reacted with a part or all of the epoxy group to introduce a (fluorenyl) acrylonitrile group. The above-mentioned production method (3) is taken as an example to more specifically describe the coating U method of the polymer (A). In the production method (3), a polymer (A) is obtained by reacting a (meth) acrylate-based polymer or copolymer having an epoxy group with an α,β-unsaturated carboxylic acid. Here, the (fluorenyl) acrylate-based polymer having an epoxy group can be obtained by using, for example, glycidyl (meth)acrylate, a (meth) acrylate having an alicyclic epoxy group (for example, daicel chemical industry). Made by a company limited by shares CycloqmeR M1〇〇'CYCLOMER a200), an epoxy group-containing (meth)acrylic acid vinegar such as 4, butyl acrylate glycidyl ether, or the like, which is obtained by separately polymerizing the raw materials, and having an epoxy group. The (meth)acrylic copolymer can be obtained by removing m (mercapto) acrylate, styrene, ethyl ethoxide, and c as the raw material of the above (meth) decenoate having an epoxy group. 200823255 Diluted nitrile, etc., without a hydroxyl group #α, β. Unsaturated monomer is used as a raw material, and two or more monomers are copolymerized. Here, if α,β-unsaturated precursor having a carboxyl group is used instead of the above-mentioned carboxyl group When the a, p_* saturated monomer is copolymerized with glycidyl (meth)acrylate, the crosslinking reaction is highly viscous or gelled, which is not preferable. The α,β-unsaturated spectabilizing acid which reacts with the above-mentioned (meth)acrylic acid s-based polymer or copolymer having an oxy group may, for example, be (meth)acrylic acid, have a carboxyl group, and

(4) Base compounds (for example, Osaka Organic Chemical Co., Ltd. manufactured by Biscott 2100). The weight average molecular weight of the polymer (A) obtained by the above production method is preferably 5, GGG 8 8 G, _, more preferably 5, _ 5 5, and is further reduced to "8 GGG 〜 35, GGG. When the average molecular weight is above 5, _, the effect of reducing the hardening shrinkage is markedly 'hardness is high at 8 〇, _ or less. The (meth) acrylonitrile equivalent of the poly(A) is 100 to 300 g/eq, Tian Lihan is also reduced to 200~3〇〇g/eq. The (meth) acryl oxime equivalent of polymer (A) is also high enough in 々 to reduce hardening shrinkage and hardness. In the above-mentioned manufacturing method (1) to (1), the polymer (A) is produced by J/two 疋 on the weight average molecular weight of the human 乂 a 3 (A) and (methacryl oxime equivalent, which can be Select the type of monomer and polymer used, the amount of 4 used, etc. ^Rili as the above-mentioned poly(methyl propane tri(methyl) molecule in the 1 fluorenyl group, having 3 or more (methyl) The acryl-based acrylate (B) may, for example, be a tri- methacrylate or a triethylene oxide-modified trishydroxypropylpropane 12 200823255 ϊ%ϊ Ester, tripropylene oxide modified glycerin acrylate vinegar, tricyclic sulfonium bromide modified 1 - (mercapto) epichlorohydrin modified glycerol tris (meth), two, dimethyl acrylate vinegar, trihydrogen嗓, three (= dilute (tetra) ' 1} 3,5-tripropyl decyl hexaol - (methyl methoxy, oxyethyl) isocyanurate, pentaerythritol di(meth) acrylate vinegar, Pentaerythritol: Ethylene pentaerythritol modified by pentaerythritol II, _ vinegar, base propyl courtyard four (a magic, dilute acid cool, two epoxy bromide modified two: Γ =!) vinegar vinegar, dipentaerythritol five (a Base 2: Limited public: 1 system:: =: yeast D 5 3 C _ "for example, 曰本化药股份. Kayala Xi D-310"), alkyl modified dipentaerythritol tetrapropylene feel δθ (for example, Japanese Pharmacopoeia Co., Ltd. "Cayadora D_") ε-caprolactone modified dipentaerythritol hexaacrylate (for example, 曰本, "Kayadora DPCA-20" manufactured by Pharmaceutical Co., Ltd.), dipentaerythritol pentamethyl Acrylic vinegar, dipentaerythritol Α (meth) acrylate vinegar, hexa-octyl oxyethylene modified sorbitol hexa (meth) acrylate, hexa (methacryloxy group, ethyl) Triphosphazene (for example, "PPZ" manufactured by Kyoeisha Chemical Co., Ltd.), etc. These may be used singly or in combination of two or more kinds. In addition, the above-mentioned polyfunctional (meth)acrylic acid I (B) When using pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, the adhesive layer is set to a hard coat film using a hardened material of the composition as a hard coat layer The surface hardness is also difficult to reduce, so it is particularly suitable. The above polymer (A) and the polyfunctional (meth) acrylate (B) 13 200823255 ratio = ratio is preferably (A) on a mass basis: (B) = 1 (four) ~ 9 〇: range of ι〇, more preferably (A) · · (B) = 2 〇: 8 〇 ~ 8 〇: range of 2 ,, further preferably (A) : (B) =: 3G : 7G ~ 7G: The range of 3G. If the compounding ratio of the above polymer (meth) acrylate (B) is within this range, the obtained cured product is less likely to cause warpage, and the adhesive layer is set to harden the composition. When the material is used as a hard coat film of a hard coat layer, the surface hardness is hard to be lowered, so that it is particularly suitable. In the active energy ray-curable resin composition, the radical polymerizable monomer (c) may be blended in addition to the above-mentioned xkb product (A) and polyfunctional (meth)acrylic acid vinegar (b). Examples of the radical polymerizable monomer (C) include N-vinyl caprolactam, N-vinylpyrrolidone, N-vinylcarbazole, vinylpyridine, acrylamide, n, n_two. Mercapto (meth) acrylamide, isobutoxy decyl (meth) acrylamide, trioctyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylamine Ethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino dimethyl octyl (meth) acrylate, acrylonitrile, lauryl (methyl) Acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (mercapto) acrylate, tetrahydroindenyl (methyl) Acrylate, ethylene diethylene glycol (metha) a Crylate, butoxyethyl (meth) acrylate, methyl glycol (meth) acrylate , phenoxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like. When the above-mentioned active energy ray-curable resin composition is blended with the above-mentioned polymerizable mono-static and polyfunctional (AA) from 200823255, the compounding amount thereof is preferably 5% by mass with respect to the above polymer (4); The total amount of vinegar (8) is 100 parts by mass, more by mass. Preferably, it is preferably 1 to the amount of the component, and the step is preferably H1. In addition, as S 1 , 卞 is the above polyfunctional (meth) group-based polymerizable monomer (enoic acid 0 曰 (B) or self-acid a monomer having an acid group such as an acid group, and an organic monomer having a (tetra), a phosphoric acid group, a sulfo group, or an alkoxytitanyl group having a monomer which burns an oxygenate楹古 is therefore better. Another - Fang A /, the adhesion of the substrate, the number of the number of 12 to ^ 'has a carbon chain, dimethyl sulphur oxygen chain, carbon, stain resistance semi-linear: key The monomer can improve the surface properties of the protective layer such as smooth surface and gas side chain adhesion, and is therefore preferred. The addition amount of the monomer is preferably "two: the original hydrocarbon chain of 2 or more... 0.01~5 mass %' is more preferably 33质量%. Eight (4) (4) excellent surface properties such as soil purity and patient adhesion, especially (meth) propionate containing gasification base, which has the following The functional group having a fluorinated fluorenyl group at the end represented by the formula (1) is more than 2 (meth)acryl fluorenyl groups, in addition to improving the surface properties, it also contributes to the improvement of the surface hardness. Thus particularly preferred to use lines of the general formula (1):

R Η •〇-CCX-Rf (1) Ο [In the formula (1), R is a hydrogen atom or an alkyl group having a carbon number of 4, and X is an alkylene chain which may have a hetero atom or is represented by the following formula (2) The linking group represented, Rf is a gasification alkyl group, and the general formula (2) is ·· 15 (2) 200823255 Ο CH2-Y-CH-C-〇-(CH^·- H2C-C-0 -(CH2^rRf1

In the formula (2), γ is a gas atom or a sulfur atom, and (5) and n may be the same or different, and may be an integer of 1 to 4, and Rf] is a fluorinated alkyl group. }] The structure represented by the above formula (1) is deteriorated by hydrolysis due to the presence of an alkyl chain or the like between the carbonyl carbon and the fluorinated alkyl group in the ester bond.

The problem is small, and the long-term stability of the properties of the cured product is excellent. Also, since the fluorinated alkyl group in the structure exists at the end of the molecule, it is not pulled as a part of the mesh at the time of crosslinking. Further, there is a -Cl group which contributes greatly to the reduction of surface tension. Therefore, for example, when used as a coating material, gas atoms can be efficiently disposed on the surface thereof, so that surface characteristics derived from fluorine atoms can be effectively exerted. Further, the fluorinated alkyl (meth) acrylate having used in the present invention must have two or more (meth) propyl sulfhydryl groups. Its in i points

In the sub-/, there are two or more cross-linking points in the hardening reaction, which are necessary for forming a firm three-dimensional network structure. Further, when the fluorine atom content in one molecule is 25% by weight or more, surface characteristics and optical characteristics from gas atoms are easily exhibited, which is preferable. When the gas atom content is 25% by weight or more, in order to exhibit surface characteristics and optical characteristics, the use of (meth)propionic acid vinegar having a fluorine-containing phenotype can be lowered, and (IV) other fluorine atom content rate is not obtained. The highly reactive compound and/or the non-reactive compound core exhibit sufficient characteristics and sufficient compatibility is obtained, and it is easy to obtain appropriate optical characteristics. Further, the molecular weight of the (meth) acrylate is preferably 500 to 4 Å. 16 200823255 When the molecular weight is in the above range, the crosslinking density is good, mechanical properties are easily obtained, and the amount of fluorine atoms which can suitably exhibit an effect can be introduced. By using such a fluorinated alkyl (meth) acrylate vinegar, the crosslinking property can be formed while the properties of the ruined atom are excellent in surface properties and optical properties of the cured product. More rigid three-dimensional net: The structure and mechanical properties (mechanical strength) are improved, and as a result, a cured product having such properties can be obtained, and a cured product excellent in hydrolysis resistance can be formed. In particular, the oxygen atom content of the (meth)acrylic acid-containing polymer having a vaporized alkyl group is preferably 25% by weight or more, and the atomic content is particularly preferably % by weight. . Further, the molecular weight is preferably from 500 to 4,000, particularly preferably from 6 to 35 Å. Further, the above-mentioned functional group and the above two or more (meth)acrylic groups independently pass through the same or different carbon atoms which may have an oxygen atom, and the alkyl chain of 5 of them is bonded to the 4-stage carbon. And a cyanurate ring or a phosphonium group, and wherein the functional group is bonded to the *-stone, dimer, or phosphorus-branched group bonded by the alkylene chain, through the above (4) The base chain is bonded to at least one of the (meth) acrylonitrile groups of V or more: 'When the three-dimensional network structure is formed, the degree of freedom in the arrangement of the joints at the cross-linking points can be 4 levels. Carbon, a cyanurate ring or a phosphonium group, and the three-eye structure itself becomes more rigid, exhibiting the mechanical properties of the hardened material, and is provided with a gasification base near the crosslinking point, and can have a hardened substance. ^Characteristics and optical properties are therefore preferred. In view of the above reasons, the above-mentioned extension chain is preferred, and particularly preferably an alkylene chain having 1 to 3 carbon atoms or an alkylene chain having 1 to 3 carbon atoms. 17 200823255 Considering that the alkylene group shown above is excellent in hydrolysis resistance of the obtained cured product, X in the general formula (1) is preferably a bond of the following general formula (3), -(CH2 ) p-zq- (CH2) r- (3) ^ [In the formula (3), z is a nitrogen atom having a hydrogen atom or a carbon number of 丨~24 alkyl group, an oxygen atom, a sulfur atom, or _nr_s〇2_ (r is the base of the gas two carbon atoms...), the singular integer, ... or;

It is an integer from 0 to 20, and 1 $ ρ+Γ$ 2〇. In particular, X in the above formula (1) is a base chain of the above formula (3), wherein the oxime is a nitrogen atom having a hydrogen atom or a carbon atom, 24 = an oxygen atom, Sulfur atom, or scratch so2_ (R is gas G or a carbon number of 1 to 24), P is 1,9 is! " is an integer of 0 to 19] or a linking group represented by the above formula (2) [wherein Rfl is _CF ("an integer of 20"), and Rf in the above formula (1) is: 1 is the same or The compound of different _cnF2n+ "integer of n胄i~2〇" is suitable for industrial production from the viewpoint of being able to be produced by a Michael addition reaction described later, and since the fluorinated alkyl group is perfluoro Since the base is burned, U can effectively exert the performance from the fluorine atom, and it is also preferable from the above aspects. In addition, when a fluorinated base other than a perfluoro ndyl group is used, it is necessary to improve the compatibility of the other components described later, and it has an effect of light transmissibility, etc., and can be effectively used for a hardened material. For the directionality and the conjugate, it is preferred to select the structure and type of the fluorinated alkyl group according to the required performance standards, uses, and the like. Further, 'Z using the above formula (3) + is a nitrogen atom having a hydrogen atom or carbon 18 200823255 atomic number 1 to 6 alkyl group, a sulfur atom, or _11_§〇^ (r is a carbon number of 1 to 6 Alkyl), or γ in the above formula (2) is a sulfur atom, Rf1 has a carbon number η of 4, 6 or 8, and Rf of the above formula ^ has a carbon number η of 4, 6 or The compound of 8 is excellent because it is particularly excellent in surface properties, optical properties, and mechanical properties. Further, R in the above formula (1) is preferably a hydrogen atom or a methyl group from the viewpoint of industrial availability of the ruthenium raw material and the production of the Michael addition reaction. The (fluorenated alkyl group-containing (meth) acrylate used in the present invention may, for example, be a compound represented by the following formula 4 (I) to (X). (I) )-C -(-CH2 ^-CtF2t+i CH2—〒H2 A R1-cch2- ch2--

CH 2· ch2· , ch2· ch2- -(OR2h o

Clock H2) Factory s-c 丨H-C 十 CH如 CtF2t+ O

1〇R2)2

CH2-C-^CH2)^CtF2t+1> O (H)

O 〇〇H2-C-fCH2)^CtF2t+1 O <0^2)i (III) [In the formula (I)~(III), R1 is a hydroxyl group, and the carbon number is 1 to 4, straight 19 200823255 chain Alkyl group, ch2=chco2ch2-, ch2=c(CH3) C02CH"h an alkanol group having 1 to 3 atoms, R2 is a (meth)acryl fluorenyl group, m and n are the same or different, and are 1~ An integer of 4, t is 4, 6 or 8, · 1 or 2, j is 2 or 3, and i+j=4.] can be CH2- 1 I - R1-CCH2- I a ch2- • (〇R4 ) i • (or2) 2 (iv) _ [In the formula (IV), R1 and R2 are the same as in the formulae (I) to (III), and the inverse 4 is HS (CH2) 2CtF2t+1 or HN (C3H7) ( CH2) 2CtF2t+i (^ where t represents 4, 6 or 8) Michael addition to (meth) propylene 醯 its m group CH] CH2- , CH〇- f0R4)_ 2· CH2* ch2- • 〇 R2) n (V) [In the formula (V), R2 and R4 are the same as those in the formulae (I) to (IV), and are 1 or 2, 11 is 2 or 3, and 11 [1+11=4.] m — Ch2 • H2C—C—c —ch2 ch2— I h2-o-ch2 - cch2 ch2- •(〇R4)pi〇R2)q -(〇H)r (VI) [in formula (VI), R2, R4 The same as in the formulas (I) to (IV), an integer of 1 to 4, q is an integer of 2 to 5 'r is an integer of 〇~3 P + q+r=6 0 ] 20 (VI!)200823255 /η2- NHC〇2CH2Cl··一^CH2-

About 2彳 —{OR% --(〇R2)w,

ch2—I 7H2 - NHC02CH2CCH20CH 辛 H2— CH2— oh2- _(or\仰\· (VIII) ch2—I 〒h2_ NHC02CH2CCH20CH2CCH2-CH2-

[In the formulae (VII) to (VIII), R2 and R4 are the same as those in the formulae (I) to (IV), w is an integer of 1 to 4, w' is an integer of 2 to 5, and w+w' = 6, y is an integer from 1 to 8, y' is an integer from 2 to 9, and y+y' = 10. Ο R2OCH2CH2, 〆CH2CH2OF^ O^N^O ch2ch2or2 (IX) [In the formula (IX), R2 and R4 are the same as those in the formula (I) (IV). CH2CH2OR4 0=Bu CH2CH20R2 (X) CH2CH2OR2 21 200823255 [In the formula (X), R2 and R4 are the same as those in the formulae (I) to (IV). Specific examples of the above-mentioned fluorine-containing alkyl (meth) acrylate include the following compounds. Each of the following specific examples is an acrylate, and the acrylonitrile group in the formula may be changed to a mercapto acrylonitrile group. Further, in the following specific examples, only R in the above formula (1) is a hydrogen atom, and one of the hydrogen atoms in the fluorenylene group bonded to the carbonyl carbon may be changed to a methyl group.

CH2OCOCH2CH2CH2CH2C4F9 hoch2—[—CH20C0CH=CH2 ch2ococh=ch2 CH2OCOCH2CH2C8F17 (ii) ch3ch2—)—ch2ococh=ch2 ch2ococh=ch2 ch2ococh2ch2ch2ch2c8f17 (iii) HOCH2—|—CH2〇COCH=CH2 ch2ococh=ch2

o CH2 (iv) H3C-CCH2-ch2--Wo-C-(CH2)rS-CH-c4CH2)rC4F9 0 cki-ch2)^c4f9

COCH=CH2) 2 O o (V) ch2- CH, bC-{CH2)2-S-CH-C-fCH2)rC6F13 o ch2- -J«^ococh=ch2) 22 (v«) 200823255 (νϋ) (ix) (x) cH2OCOCH2CH2SCH2CH2C4F9 HOCH2-I ~ ch2ococh = ch2 ch2ococh = ch2 ch2ococh2ch2sch2ch2c4f9 ch3ch2-1-ch2ococh = ch2 ch2ococh = ch2 3h7 ch2ococh2ch2nch2ch2c8f17 hoch2- |? -ch2ococh = ch2 ch2ococh = ch2 ch2ococh2ch2sch2ch2c8f17 ch3ch2- | -ch2ococh = ch2 ch2ococh =ch2 ch2ococh2ch2sch2ch2c4f8h ch3ch2-—^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ -(〇C2H4)s-OCOCH=CH2 in2-(OC2H4}t_OCOCH=CH2 r+ s+t = 3 (xHi) C2H5OCO-CH2- OCOCH=CH2 ch2 ch2—ococh=ch2 ch2ch2—)—ch2—〇coch2ch2sch2ch2c8f CH2 CH2 —OCOC2H5 , OCOC2H5 17 23 200823255 (xiv) (xv) CH2· CH2- ch2-ch2- c2h4- , 〇2Η4» C2H4-C2H4- •OCOCH2CH2SCH2CH2C8Fd ^OCOCH=CH2) ten coch^cWsF,) 1 j〇COCH=CH2 ) ococh=ch2 CH2 CH2 ——OCOCH2CH2SCH2CH2C6F13 (xvi) CH3CH2-|—CH2〇CH2 ch2ch3 ch2 ch2——ococh=ch2

〇COCHsCH2 /OCOCH2CH2SCH2CH2C8F17 ?H2 ch2 —〇coch2ch2sch2ch2c8f17 (xvii) CH3CH2-j—CH2OCH2-[—CH2CH3 CH2 ch2 ——ococh=ch2 , ococh=ch2 /OCOCH2CH2SCH2CH2C8F17 ch2 ch2 ——OCOCH2CH2SCH2CH2C8F17 {xvi"} HOCH2-1CH2〇CH2&quot ;"|~CH2—〇COCH=CH2 ch2 ch2 — ococh=ch2 , ococh=ch2 /ococh=ch2 ch2 ch2——OCOCH2CH2SCH2CH2C6F13 (xix) hoch2—[^ch2och2-|—ch2——OCOCH2CH2SCH2CH2C8F17 ch2 ch2—ococh =ch2 , ococh=ch2 ococh=ch2 "zhen ch2 ch2 ococh2ch2sch2ch2c8f17 H2C=HCOCO - CH2-j~CH2OCH2-|~<iH2 — 〇c〇CH2CH2SCH2CH2C8F17 ch2 ch2-ococh=ch2 ic〇CH2CH2SCH2CH2C8F17 OCOCH2CH2SCH2CH2C8F17 ch2 〒H2-〇COCH2CH2SCH2CH2C8F17 H2c=hcoco-ch2—[—ch2och2-|—ch2-ococh=ch2 ch2 ch2

I I ococh=ch2 ococh=ch2 24 (xxi) (xxii)200823255 CH2OCOCH2CH2SCH2CH2C4F9 ΝΗΟΗ2〇2^Η2〇~CH2〇C〇CH2CH2SCH2CH2C4Fg < ch2ocogh=ch2 (xxiii)

\:, Nhco2ch2c <pH2OCOCH2CH2SCH2CH2C4F9 \ -CH2OCOCH2CH2SCH2CH2C4F9 ch2ococh = ch2 CH2OCOCH2CH2N (C3H7) CH2C6F13 nhco2ch2c it "CH2OCOCH2CH2N (C3H7} CH2C6F13, ch2ococh = ch2 ch2ococh2ch2n (c3h7) ch2c6f13 hco2ch2c-ch2ococh = ch2, ch2ococh = ch2 / CH2OCOCH2CH2SCH2CH2C8F17 nhco2ch2c- ~ CH2OCOCH2CH2SCH2CH2C8F17, Ch2ococh=ch2 ch2ococh2ch2sch2ch2c8f17 nhco2ch2c^—ch2ococh=ch2 ch2ococh=ch2

(xxiv)

Ch2o&lt; coch=ch2 (XXV)

CH2OCOCH2CH2SCH2CH2C8F17 nhco2ch2cch2och2 this ch2ococh = ch2 ch2ococh2ch2sch2ch2c8f17 ch2ococh = ch2 ch2ococh = ch2 (JH2OCOCH2CH2SCH2CH2C3F17 NHC02CH2CCH2〇CH2CCH2〇COCH = CH2 ch2ococh2ch2sch2ch2c8f17 ch2ococh = ch2 25 200823255 Ο (xxvi) CH2 = CHC〇2CH2CH2 &gt; .nAsn ^ o CH2CH2〇COCH2CH2SCH2CH2C6F13 people who 〒 ch2ch2ococh. =ch2 ο (xxvii) CH2=CHC02CH2CH2^nJIVnXCH2CH2OCOCH2CH2SCH2CH2C8F17

O^N^O CH2CH2OCOCH=CH2 o

(xxviii) CH2=CHC02CH2CH2, daughter-in-law CH2CH2OCOCH2CH2SCH2CH2C4F8H

O^N^O CH2CH2OCOCH=CH2 ch2ch2ococh2ch2sch2ch2c6f13 (xxix) o=p-ch2ch2ococh=ch2 ch2ch2ococh=ch2 ch2ch2ococh2ch2sch2ch2c8f17 (XXX) 0=P-CH2CH2〇COCH=CH2 ch2ch2ococh=ch2 as the above-mentioned fluorine-containing alkyl group The method for producing the acrylate is not particularly limited, and examples thereof include a method of synthesizing a compound containing three or more (meth) acryloyl groups with a compound having a fluorinated alkyl group and an active hydrogen by a Michael addition reaction. Or using an alkyl carboxylic acid having a fluorinated alkyl group, a polyhydric alcohol, and (meth)acrylic acid as a raw material, and adding a polymerization inhibitor such as hydroquinone in the presence of an acid catalyst such as hydrochloric acid or sulfuric acid at 80 to 120 ° C. A method in which a condensation reaction is carried out, and the reaction is carried out for 3 to 10 hours while removing moisture generated by the reaction. In particular, the above-mentioned production method using the Michael addition reaction is a by-product formed by the reaction because it is an addition reaction of 26 200823255, and can be carried out under mild conditions as described later, and the gas atoms in the molecule can be easily adjusted. Since the content rate and the number of functional groups of the (meth) acrylonitrile group are, for example, a method of obtaining a fluorinated alkyl group-containing (meth) acrylate used in the fluorinated photocurable composition of the present invention is preferred.

Further, the monomer having a dimethyl methoxyalkylene chain is excellent in surface smoothness and the like, and as the monomer, for example, it is preferable to use an alkyl group such as an ethyl group or a propyl group. An acrylate or the like having a (meth) acrylonitrile group introduced into the spacer formed by the substrate. These acrylates can be cited byk-chemie

BYK-UV3500 and BYK-UV3570 manufactured by the company, Ebecryll3 60 manufactured by diacel.UCBUCB Co., Ltd., etc. Further, in the active energy ray-curable resin composition, an amine ester ruthenium acrylate (D) may be blended as a component other than the above (A) to (c), and the component (D) is a polyisocyanate. And have in one molecule! An addition reaction of a base and two or more (meth)acrylic acid acrylates (d2). The polyisocyanate vinegar (dl) may, for example, be 2,4•toluene diisocyanate, 2,6-toluene diisocyanate, 1&gt;3·xylene diisocyanate, 4,4 , an aromatic isocyanate compound such as diphenyl diisocyanate, hydrazine, 5 · naphthalene diisocyanate or 4,4,-diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, Isophorone diisocyanate, borneol, diisocyanate, nitroxylene diisocyanate, hydrogenated methylene diphenyl phthalate, M·cyclohexene Diisocyanate S is a compound having two linoleic acid groups bonded to an alicyclic hydrocarbon (hereinafter referred to as alicyclic diisocyanate), trimethylene 27 200823255 2 and fat The aliphatic diisocyanate may be a compound having a bonded isocyanate group such as diisocyanate or hexamethylene diisocyanate (hereinafter referred to simply as vinegar). These polyisocyanates can be used alone or more. Further, among the polyisocyanates (dl), aliphatic diiso-ampacid esters or alicyclic diisocyanates are preferred, and isophorone diisocyanate random norbornane diisocyanate or hydroxylene diisocyanate is preferred. Hydrogenated methylene

Diphenylene diisocyanate and hexamethylene diisocyanate. The best is the ice isocyanate diisocyanate. The acrylate (d2) which has a hydroxy group and a (meth) propylene group in one molecule used in the present invention may, for example, be a trimethylolpropane bis(indenyl) acrylate. And a polyacrylate of a compound containing a polyvalent hydroxyl group such as pentaerythritol tri(meth)acrylate or dipentaerythritol penta(meth)acrylate, and an adduct of the polyacrylate and caprolactone. And an adduct of such polyacrylates and alkylene oxides, epoxy acrylates, and the like. These acrylates (d2) may be used singly or in combination of two or more. Among the acrylates (d2), an acrylate having 1 L group and 3 to 5 (meth) acryl fluorenyl groups in one molecule is preferred. Such an acrylonitrile may, for example, be pentaerythritol triacrylate or dipentaerythritol pentaacrylate. Therefore, it is particularly preferable because a hardened film having a high hardness can be obtained. The amine ester acrylate (D) used in the present invention is reacted by adding the two components of the above polyisocyanide I ^ ( dl ) and the above acrylate (d2 ). The ratio of the hydroxyl equivalent of the above acrylate (d2) to the equivalent of one equivalent of isocyanate in the polyisocyanate 28 200823255 acid vinegar (di) is usually preferably 〇1 to 5 Å, more preferably 0.1 to 10, further preferably It is 0·9~12. Further, the reaction temperature of the above polyisocyanuric acid (dl) and the above acrylate (d2) is preferably from 3 〇 to 15 〇 C, more preferably from 50 to 10 ° C. Here, the end point of the reaction can be confirmed by, for example, disappearing the infrared absorption spectrum of 225 〇cm-i of the isocyanate group or by determining the isocyanate group content by the method described in JIS K 7301-1995 to shorten the reaction time. For the purpose of the above-mentioned addition reaction, the use of a catalyst as a catalyst may, for example, be an alkaline catalyst (an amine such as pyridine, pyrrole, diethylamine, diethylamine, dibutylamine or ammonia). , butyl phosphine, triphenylphosphine and other phosphines), acidic catalyst (cyclic succinic acid copper, sulphuric acid, sulphuric acid, tributoxy sulphate, tetrabutyl sulphate, butyl sulphate, titanium A metal alkoxide such as butoxy hydrazine, a Lewis acid such as aluminum chloride, or a tin compound such as #^^butyltin dilaurate or dibutyltin diacetate. i) 〆 and zhongzhong are good as acidic catalysts, and then they are taken as tin compounds. The catalyst is usually added in an amount of 0.1 to 1 f relative to the 丨〇〇 λ Λ t t. If necessary, it can also be used as a solution of acetic acid, ethyl acetate, methyl ethyl _ _ 笙, 丨 丨 暴 暴 丁基 butyl ketone, bad ketone ketone or no isocyanic acid Monomer Example + μ, + . ^ The radical polymerizable property of the P-position of the cross-linking_the radically polymerizable monomer (c) and the monomer of the guanamine group is used as a solvent. These kinds of dissolved/worked soils can also be used in two or more types. The body can be used alone in the range of the molecular weight of the above amine ester acrylate (D). Molecularly-named Okasri 杈 为 is 500~1,500 knives in the case of Haikanwei, due to the temperable film, hardening # shrink _ fm, Ding Θ high hardness hard 收 细 fine &amp;: small Therefore, the star can be reduced, and the hard film of the hard film 29 200823255 is curled. When the above-mentioned amine ester acrylate (D) is blended in the above-mentioned active energy ray-curable resin composition, the compounding amount thereof is 1 〇 with respect to the total of the above polymer (a) and polyfunctional (fluorenyl) acrylate (B). The mass part is preferably from 1 to 100 parts by mass. In the present invention, when the above-described active energy ray-curable resin composition is used as a hard coating agent, a hardened material is obtained by irradiating an active energy ray. The active energy ray includes ionizing radiation such as ultraviolet rays, electron rays, alpha rays, beta rays, and gamma rays. Further, when the resin composition is cured by ultraviolet rays, a photopolymerization initiator is added to the active energy ray-curable resin composition. A photosensitizer can be further added if necessary. On the other hand, when ionizing radiation such as electron beam, ?-ray, ?-ray, or gamma-ray is used, even if a photopolymerization initiator and a photosensitizer are not used, it is rapidly hardened. Therefore, it is not necessary to add such a substance. When curing by ultraviolet rays, an effective photopolymerization initiator can be roughly classified into an intramolecular cracking type photopolymerization initiator and a hydrogen-abstracting photoinitiator. Examples of the intramolecular splitting type photopolymerization initiator include diethoxyethyl benzene, 2 hydroxy-2-methylphenylpropan-1-one, benzyl dimethyl ketal, and κ (real Propyl phenyl) hydroxy-2-methylpropanone, 4_(hydroxyethoxy)phenyl _ (2•hydroxy-2-propyl) ketone, “hydroxycyclohexyl phenyl ketone, 2 fluorenyl morpholine Ethyl benzene compounds such as thiolmethyl phenyl) propane ketone, 2-benzyl dimethyl amide 丨 ( ( (4 morpholinophenyl) butanone, benzoin, benzoin methyl ether Benzoin compound such as benzoin isopropyl ether, 2,4,6-trimethylbenzylidene 30 200823255 Diphenyl money oxide, bis(2,4,6-trimethyl benzamidine) Terpenylphosphine oxide compound such as phenyl phenyl sulphate, benzophenone, ▼ phenylglyoxylate, oligo-2-yl-2-methyl·Η4·(1_methyl Ethyl phenyl) propyl steel, bro [4-(2-carbylethoxy) phenyl] 2 _ yl 2 _ _ _ _

A compound having a small 2-base group such as {4·[4_(2•transyl-2-f-propionyl)-f-yl]-phenyl R-methyl-propan-1-one.

On the other hand, examples of the dehydrogenation type photopolymerization initiator include benzophenone, methyl benzylidene benzoate, β4β phenyl benzophenone 4, 4, dichlorobenzophenone, and a thiol group. Benzophenone, 4-benzylidene- 4,-methylphenylsulfonate, benzophenone, 3,3,,4,4,_tetra(t-butylperoxy)phenyl Benzophenone-based compounds such as ketone, 3,3'-dimethyl-4-methoxybenzophenone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2, Renji Ethyl thioxanthone, 2, dimethyl thioxanthone thioxanthone, Michler, s "amino benzophenone such as 丨 (10), 4,4'-diethylaminobenzophenone Compound, 1〇-butylchloroacridone, 2-ethylhydrazine, 9, quinone phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, oxy-phenyl-acetic acid 2-[2- a compound such as a mixture of oxy-2-phenyl-ethoxycarbonyl-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester, etc. The photosensitizer of the active energy ray-curable resin composition used in the present invention is not particularly limited, and examples thereof include an amine such as an aliphatic amine or an aromatic amine. a class of ureas such as o-phenyl thiourea, sodium thiodithiophosphate, S, a sulfur compound such as benzyl isoflavone-p-toluenesulfonate, etc., relative to an active energy ray-curable resin composition 100 parts by mass of the resin component, the photopolymerization initiator and the photosensitizer are preferably used in an amount of from 0.12 to 20% by mass, more preferably from 0.5 to 10% by mass, more preferably from 0.5 to 10% by mass. The active energy ray-curable resin used in the composition is composed of various additives, and may be dissolved as needed. Examples of the addition of hydrazine include a polymerization inhibitor, an antioxidant, a bismuth bis-: a coating agent, and a coating surface improving agent ( Wetting property, slidability improver, etc.), 曰i诏, coloring agent, inorganic fine particles, etc. As inorganic fine particles, it can be exemplified by titanium, DX, oxidized, oxidized, oxidized, oxidized, oxidized, oxidized, oxidized A metal oxide such as a metal oxide such as a tin oxide or a tin oxide. The average particle diameter of the upper and lower particles is 1 μm or less, preferably 300 nm or less, more preferably 100 nm or less. Adhesiveness of a film base material, etc. For the TF, modified rosin, polymerized rosin, arsenic resin, alkane: genus resin, etc., fragrant bean 茚 、, 舫 舫 烃 hydrocarbon, _ fat, etc. can also be used (4) (4) h can also be used. (4) Modified resin. The content of the solvent used for the dilution of the beryllyl group may include an alcohol such as toluene or xylene, ethanol, or (iv) an alcohol, acetic acid w, acetic acid, and a diacetate. Ester, methyl ethyl ketone, methyl isobutyl ketone, ring: nam ketone, etc. These solvents may be used singly or in combination of two or more kinds [manufacturing method of hard coat film], and the present invention The protective adhesive film can be produced by coating a film of the radiation hardening resin composition on the film substrate and hardening it to form a hard 32 200823255 coating to form a hard coating film, and then on the film substrate. The opposite side of the surface having the hard coat layer forms an adhesive layer. Examples of the method of applying the active energy ray-curable resin composition to the film substrate include gravure coating, roll coating, comma coating, air knife coating, light touch coating, and spray coating. Hanging coating, dipping coating, spin coating, brush coating, integral coating by wire mesh, wire bar coating, flow coating, and the like. Further, it may be a printing method such as lithography or letterpress printing. Among them, gravure printing, roll coating, comma coating, air knife coating, light touch coating, wire bar coating, and flow coating are preferred because a coating film having a relatively constant thickness can be obtained. In the apparatus for irradiating active energy rays, when ultraviolet rays are used, examples of the light generating source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal-based lamp, an electrodeless lamp (molten lamp), a chemical lamp, a black light k, and a mercury. - Xenon lamps, short arc lamps, cesium-cadmium lasers, argon lasers, sunlight, LEDs, etc. Further, when the active energy ray-curable resin composition used in the present invention is applied onto a film substrate to form a cured film, if a xenon flash lamp irradiated by a flash method is used, the thermal influence on the film substrate can be reduced. Therefore, it is preferred. The thickness of the hard coat layer used in the present invention can be suitably adjusted to a thickness of 5 to 25 μm in order to suitably exhibit a hard coat function when a protective adhesive film having a total thickness of 150 μm or less is formed. It is preferably 5 to 2 μm, more preferably 5 to 15 μm. When the thickness is less than 5 μm, the surface pencil hardness is lowered. When the thickness exceeds 25 μm, the adhesion of the hard coat layer is difficult to apply. [Hard Coating Film] 33 200823255 The hard coating film used in the present invention has at least the above-mentioned film substrate and hard coat layer when it is laminated on a display portion of an image display device for use in a mobile phone, etc. From the viewpoint of exerting an anti-damage effect, the pencil hardness of the surface of the hard coat layer is at least 3H or more, preferably 4H or more. When it is less than 3H, when the glass panel is laminated via the adhesive and the hard coat film of the present invention, the surface erroneous hardness is lowered. Further, the light transmittance of the hard coat film is preferably 85% or more, more preferably 90% or more. Further, in order to improve the adhesion to the hard coat layer, a thin undercoat layer may be provided on the surface of the film substrate in a range of not more than 150 μm in total thickness. [Adhesive Layer] As the adhesive layer used in the present invention, an adhesive layer having a thickness of 5 to 20 μm is used. In the present invention, by setting the thickness of the adhesive layer to the thickness, the yoke can sufficiently adhere to the object to be adhered, and at the same time, even if stress concentration occurs on the surface of the protective adhesive film, it can be kept high. The protective modulus of the entire adhesive film is considered to be such that the hardness of the hard coat layer provided on the surface of the adhesive film of the adhesive film can be suppressed from being lowered. As the adhesive for the adhesive layer used in the present invention, a known acrylic, rubber or ketone-based adhesive resin can be used. Among them, from the viewpoint of light resistance and heat resistance, an acrylic copolymer containing a repeating unit derived from an acrylate having 2 to 14 carbon atoms is preferred. For example, a bismuth acrylate copolymer containing a repeating unit derived from n-butyl acrylate, isooctyl acrylate, 2·ethylhexyl acrylate, isodecyl acrylate or ethyl acrylate may be mentioned. Further, the repeating unit is preferably a repeating unit containing an acrylate having a hydroxyl group at a side chain, a carboxyl group such as 34 200823255 or a polar group such as an amine group, or another vinyl monomer, in a range of ο·01 to 15% by mass. The acrylic copolymer can be obtained by copolymerization using a &amp; solution polymerization method, a monolithic polymerization method, a suspension polymerization method, an emulsion polymerization method, a 4′′, or a spray electron beam irradiation method. The average molecular weight of the acrylic copolymer is preferably. For 4 million, better for ~1.2 million.

▲ Further, in order to increase the cohesive force of the adhesive, it is preferred to add a crosslinking agent. Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, and a chelate crosslinking agent. The amount of the crosslinking agent to be added is preferably adjusted so that the gel fraction of the adhesive layer becomes 〜25 to 80%. A more desirable gel fraction is 4 g to 75%. The most preferable one is 50 to 70%. When the gel fraction is less than 25%, the surface hardness of the adhesive film is lowered when the protective adhesive film is adhered to the panel. On the other hand, when the condensation rate exceeds j 8G%, the adhesion will decrease. The aged adhesive layer was placed in toluene, and the dry mass of the insoluble component remaining after standing for 24 hours was measured, and the gel fraction was expressed as a percentage of the original mass. Further, in order to increase the adhesion of the adhesive layer, an adhesive imparting resin may be added. Adhesive property added to the adhesive layer of the adhesive tape of the present invention: rosin-based resin such as rosin and rosin esterified product, diterpene polymerization =, α-pinene-phenol copolymer, etc. The olefin resin, the aliphatic resin (1), the petroleum resin such as the aromatic resin (C9), and the styrene resin, the phenol resin, the xylene resin, and the like. In order to make the b* value of the adhesive layer after the battle place = day is 6 or less, it is preferable to add a hydrogenated rosin having less unsaturated and less bonds, an esterified product of uneven rosin, or an aliphatic scented petroleum resin. . , Fang 35 200823255 In order to achieve both adhesion and yellowing resistance, it is preferred to use both high rosin ester and polymerized rosin ester and petroleum resin. In the case where the adhesive resin is a propionic acid copolymer, the phase (10)f parts of the acrylic copolymer is preferably from 0 to 60 parts by mass. When attaching importance to adhesion, it is best to add ~% beri injury. In addition, when the adhesive resin is a rubber-based resin, it is preferable to add 8 to 15 parts by mass of the adhesive resin to the rubber-based resin. . When the "reagent resin is cut as a (4) grease, the imparting resin is generally not added. In addition to the above components, a known and customary additive may be added to the adhesive. For example, in order to carry out the bonding of the glass with the glass. Sex, you can add 0.0 0 1~0 · 0 0 5 range of stone eve detection value 十 f f 囷旳 烷 偶 偶 耳 耳 耳In addition to this, a plasticizer, a softener, a filler, a pigment, a flame retardant, or the like may be added.黏 The adhesive layer can be formed on the film substrate by a method generally used for coating an adhesive sheet. The composition of the adhesive layer may be directly applied to the substrate film and dried, or may be applied to the F Α &lt; 、, i.e., the P-piece (release sheet), and dried to the substrate film. ° The adhesive used as the adhesive layer can adjust the stress relaxation of the adhesive in a high temperature environment by setting the dynamic elastic modulus of the dynamic viscoelastic spectrum 纟m: at a frequency of 1 Hz to i 〇 xi 〇 5 Pa or more. The foaming of the adhesive layer at a high temperature is suppressed. Storage caps #批^ The upper limit of the number of tweezers is not particularly limited as long as it can modulate the range of the adhesive, but from the practical adhesion and prevention of overflow during processing; t, &gt; w軏仏5.5xl〇5Pa or so, especially good 3.0

Xl05Pa below. 36 200823255 In addition, the dynamic viscoelastic spectrum of the adhesive used as the adhesive layer at the frequency mz is 2 (the storage elastic modulus of the TC is preferably ι 〇χΐ〇 5 ι ^ : , more preferably 2.5 x 1 G 5 Pa or more. When the storage elastic modulus is gamma or more, the surface hardness of the protective adhesive film caused by the adhesive can be suitably suppressed. [Protective Adhesive Film] The protective adhesive film of the present invention is provided with an adhesive on the hard coating film. And a protective film having a total thickness of 6 〇 15 15 μm, preferably 8 〇 12 12 μm. The protective medium of the present invention is formed by combining the physical property values of the constituent members in a specific range. It is possible to achieve the opposite characteristics of the film which is extremely thin (9) micrometers or less. It is possible to prevent the damage and the deformation at the time of stress concentration. Therefore, even if a hard coat layer having a high hardness and rigidity is not provided, the base material is not provided. Further, it is possible to achieve an excellent surface hardness which is not obtained by the conventional protective film. Further, since the protective film of the present invention can be used without sticking to a hard coat layer and a film base material having extremely high hardness and rigidity, even if it is attached to a sticker In the case of the image, it is also difficult to cause peeling due to repulsion. The protective adhesive film of the present invention can achieve high surface hardness even when it is adhered to the adhesive object through the adhesive layer, and is bonded to the glass. In the state, it is possible to achieve a hardness of preferably 2H or more, more preferably 3H or more. It can be suitably used as a protective film for a thin glass panel of a portable electronic terminal and a protective film for various displays. In the case of a glass-coupled object that causes cracking, it can be effectively used as a scattering preventing film that prevents scattering when the adhering object is broken. 37 200823255 The protective adhesive film of the present invention has a peeling adhesion force (10). Tensile grip 3G - for the above range, for portable type, 2N: 25mm. By peeling the adhesive adhesion film from the end. Also 'Too: It is difficult to occur when the machine is known to have a protection ratio of 85. More than %, and more clearly, the light-shielding of the protective adhesive film is grasped, and the image display device is made good by the visibility of the visible portion of the light transmittance. [Screen panel]

The screen panel of Maoyue is composed of a laminate of a glass plate and a protective adhesive film of the present invention. Since the screen panel is difficult to be damaged on the surface layer, it can be effectively used for the image display portion for various displays, especially in the state of being combined with a glass plate, and having a surface hardness of 3H or more. Adhesive film The laminated body of the glass plate, which is a screen panel, is greatly reduced in privateness due to damage of the glass plate, and thus can be used extremely effectively for various display applications having the screen panel on the surface of the image display portion. The glass plate is preferably a tempered glass plate. As a method of strengthening a glass plate, a physical strengthening method and a chemical strengthening method are mentioned. In particular, chemical strengthening methods include ion exchange and air-cooling. The material of the glass plate may be, for example, float glass, alkali glass, alkali-free glass, or tempered glass. [Portable electronic terminal device] The portable electronic terminal device of the present invention is configured to be a casing having a liquid crystal display module (LCD Module), and the laminated body of the protective film of the present invention is a screen panel and a liquid crystal display. The surface of the module is fixed across the gap (Figure 1). In this configuration, since the gap portion is provided in the lower portion of the screen panel, the screen panel on the surface of the image display portion is bent when an impact is applied to the surface of the screen panel. When the bending occurs, stress is concentrated on the concave portion, and damage is caused. However, even in such a case, the film can be suitably prevented from being damaged by the (4) film of the present invention. Therefore, the protection of the present invention = = the curtain panel can be particularly suitable - in this configuration of the portable electric: = 疋 疋, as a mobile phone with a portable glass. Due to the pockets and bags of the pants

The surface of the mobile phone that we carry is easy to be damaged, so it will be able to reduce the visual display of the image display portion by attaching the protective adhesive film of the present invention to the screen panel of the invention. Therefore, it is preferred to use it. [Embodiment] The present invention will be more specifically described by the following examples and comparative examples, but the present invention is not limited to the examples. (Synthesis Example 1) <Synthesis of Polymer (Α1)> In a flask equipped with a mixer, a gas introduction tube, a cooling tube, and a thermometer, 25 μM portions of glycidyl methacrylate (hereinafter referred to as GMA), 1.6 were added. Parts by mass of lauryl mercaptan, drawing parts by mass of methyl isobutyl ketone (hereinafter referred to as ΝΟΒΚ) # 7.5 parts by mass 2,2,_azobisisodin (hereinafter referred to as ΑΙΒΝ), mixing under nitrogen flow While heating for 1 hour, the reaction was carried out at % °c for 1 hour. Next, a mixed liquid of 750 parts by mass of GMa, 4.4 parts by mass of lauryl mercaptan, and 22 5 parts by mass of ΑΐβΝ was added dropwise at 2 hours while rc (tetra) was added, and then reacted for 3 hours in _. Then, ι〇39 was added. 200823255 parts by mass of AIBN, and then reacted at i〇0 °C for 1 hour, then the temperature was raised to 12 (about rc 'reaction for 2 hours. Cooled to 6 ° ° C, the nitrogen introduction tube was replaced with an air introduction tube, and 507 parts by mass of acrylic acid was added. (hereinafter referred to as AA), 2 parts by mass of p-methoxyphenol, and 5.4 parts by mass of triphenylphosphine, and after mixing, the reaction liquid was bubbled while raising air to ll ° C for 8 hours. 1.4 parts by mass of p-methoxyphenol was added, and after cooling to room temperature, MIBK was added so that the nonvolatile content was 50% by mass, and the polymer (A1) (MIBK solution having a nonvolatile content of 50% by mass) was obtained. The polymer (A1) had a weight average molecular weight of 11, 〇〇〇 (calculated by GPC in terms of polystyrene), and a (meth) acrylonitrile equivalent of 300 g/eq. (Synthesis Example 2) <Polymer (A2) Synthesis > with a mixer, gas introduction tube, cooling tube and temperature The flask was charged with 200 parts by mass of GMA, 50 parts by mass of n-butyl methacrylate (hereinafter referred to as ηΒΜΑ), 1.8 parts by mass of lauryl mercaptan, 1000 parts by mass of MIBK, and 7.5 parts by mass of hydrazine, and stirred under a nitrogen stream. The temperature was raised to 90 ° C over 1 hour, and reacted at 90 ° C for 1 hour. Then, 600 parts by mass of GMA, 150 parts by mass of ηΒΜΑ, and 4.8 parts by mass of lauryl mercaptan were added dropwise over 2 hours while stirring at 90 ° C. 22.5 parts by mass of a mixed solution of hydrazine was then reacted at 100 ° C for 3 hours. Then, 1 part by mass of hydrazine was added, and after reacting at 100 ° C for 1 hour, the temperature was raised to about 120 ° C for 2 hours. At 60 ° C, the nitrogen introduction tube was replaced with an air introduction tube, and 406 parts by mass of AA, 2 parts by mass of p-methoxyphenol, and 5.4 parts by mass of triphenylphosphine were added and mixed, and the reaction liquid was bubbled with air. The temperature is raised to 11 〇 ° C, and the reaction is 200823255 8 J. After Ik, L4 parts by mass of p-methoxybenzene is added, and after cooling to room temperature, MIBK is added to make the non-volatile component 50% by mass, and polymerization is obtained. (non-volatile content of 50% by mass of MIBK solution). Here, The weight average molecular weight of the mouth material (A2) is 8,8 〇〇 (obtained by Gpc using water styrene exchange), and the (meth) propyl ketone base equivalent is (four) ^. (Synthesis Example 3) Synthesis of alkyl acrylate (average addition functional group number 2) &gt; In a 20 〇 ml reaction flask, after dropwise addition at room temperature with stirring ^ (1 mol) perfluorooctyl ethyl thiol at 28 9g (〇〇5m〇i) dipentaerythritol octaacrylate (LUMICURE DPA-_ manufactured by Dainippon Ink Chemical Industry Co., Ltd.), mixed solution of 1.0 g of triethylamine and 20 g of methyl isobutyl ketone (MIBK) . After the completion of the dropwise addition, the mixture was further stirred at 5 (rc for 3 hours, and MIBK and triethylamine were distilled off under reduced pressure using an evaporator (bath temperature: 5 〇〇c or less) to obtain 76 8 g of a product (A3). It is composed of a mixed composition containing the fluorinated alkyl group-containing acrylate represented by the above structural formula (xxi) and further containing an propylene group and a perfluorooctylethyl thiol addition reaction site and the above structure. Compounds of different formula (xxi) were confirmed. The desired synthesis was confirmed based on the peak and integral values of the 1H-NMR spectrum of the product. W-NMR : δ 2.20-2.90 ( m 5 16H ) 3 ·30-3 ·50 ( m , 4H ) 200823255 4·10_4.40 ( m,12H) 5·84 ( d, J=l〇.2Hz, 4Η) 6·10 ( dd, J=l〇.2,17·2Ηζ, 4H) 6· 42 ( d,:Γ=17·2Ηζ, 4H) (Preparation of hard coating agent (1)_) Mix 100 parts by mass of MIBK solution of polymer (A1) synthesized in Synthesis Example i (nonvolatile component 5) 〇% by mass), 50 parts by mass of pentaerythritol tetraacrylate (hereinafter referred to as PET A), and 1 part by mass of acyl fluorene acetonide compound (diCel hexaaerylate) Co., Ltd. manufactures Ebecryl, hereinafter referred to as siA) and 4 parts by mass of a photopolymerization initiator (hydroxycyclohexylphenylhydrazine, hereinafter referred to as HCPK), and then diluted with ethyl acetate to a nonvolatile content of 4% by mass. Hard coating agent (1) (Preparation of hard coating agent (2)) 100 parts by mass of MIBK solution of polymer (A2) synthesized in Synthesis Example 2 (nonvolatile content: 50% by mass), 50 parts by mass of PETA 1 is a portion of SiA and 4 parts by mass of HCpK, and then diluted with ethyl acetate to a nonvolatile content of 40% by mass to obtain a hard coating agent (2). (Preparation of hard coating agent (3)) uniformly mixed 1〇〇 The MIBK solution (50% by mass of the nonvolatile component) of the polymer (ai) synthesized in the synthesis, 50 parts by mass of pentaerythritol propylene (hereinafter referred to as PETA), and 1 part by mass of the above synthesized A3 ( Synthesis Example 3) and 4, for example, HCPK, and then diluted with ethyl acetate to a nonvolatile content of 40% by mass to obtain a hard coating agent (3) 42 200823255 (Production of hard coating film (1) Applying on one side of a polyethylene terephthalate film having a modulus of elasticity of 4.5 GPa and a thickness of 75 μm The prepared hard coating agent (work), after drying for 6 seconds at 6 〇t: in an air atmosphere, using an ultraviolet irradiation device (radiation ultraviolet system, manufactured by Japan Co., Ltd. rF45〇), lamp: 12〇w/ Cm, Η valve) irradiated with ultraviolet light by irradiation amount 〇5J/cm2 to form a thickness of 8 μm more: k layer, followed by surface treatment of the non-hard-coated surface by a corona treatment device, so that the surface tension is 55 dyne/cm, Thus, a hard coat film (1) was obtained. (Production of Hard Coating Film (2)) A hard coating film (i) used in place of the above-described hard coating film (1) was produced, and a hard coating film was obtained in the same manner except that the hard coating agent (2) prepared above was used. (2 ). (Production of Hard Coating Film (3)) The above-prepared hard coating agent (η, at 6〇c&gt; was applied to one surface of a polyethylene terephthalate film having a modulus of elasticity of 4.5 GPa and a thickness of 75 μm. c After drying for 90 seconds, use an ultraviolet irradiation device in an air atmosphere ("F45" manufactured by Japan External Co., Ltd., Japan: Co., Ltd., lamp: i2〇w/cni, Η valve) to know the amount of light 〇5J /cm2 was irradiated with ultraviolet rays to form a hard coat layer of thickness. Then, the surface of the non-hard-coated surface was subjected to a surface tension of 5 5 dyne/cm by a corona treatment device to obtain a hard coat film (3). Preparation of Hard Coating Film (4)) A hard coating agent (1) was applied to one side of a polyethylene terephthalate film of a coating weight of 4.5 GPa and a thickness of 50 μm, and dried for 9 seconds. 200823255 Moxibustion is used in a working-hole atmosphere under ultraviolet light irradiation (under the jurisdiction of the deep ultraviolet system. Manufactured by Japan Co., Ltd., lamp: (10)/(10), Η... irradiated with ultraviolet light at a light amount of 0.5 J/cm2 to form a hard coat layer of thickness. Then, the surface of the non-hard-coated surface is surface-treated by a corona treatment device, so that the surface The surface tension is 55dyne/em to obtain a hard coating film (4). (Preparation of hard coating film (5)) Filming of polyethylene terephthalate with a modulus of 4.5 GPa and a thickness of 75 One surface is coated with a hard coating agent (1), and after drying for 9 seconds, an ultraviolet irradiation device (light deep ultraviolet system, manufactured by Japan Co., Ltd. F45 (), lamp: 12 () w/em, H valve) irradiates ultraviolet rays and lines with an amount of light of 0.5 JW to form a hard coating of a thick t-shirt. The surface of the non-hard-coated surface is treated by a corona treatment device so that the surface tension is 55 dyne/cm. Thus, a hard coat film (5) is obtained. (Production of hard coat film (6)) ^A film made of polyethylene terephthalate® having a modulus of elasticity of 4.5 GPa and a thickness of 5 〇μΐη, The non-hard-coated surface of the hard coat film (surface pencil hardness: 3 Å) manufactured by Toray Film Processing Co., Ltd. having a hard coat layer having a thickness of 2 μm was surface-treated by a corona treatment device so that the surface tension was 55 dyne/cm. Thus, a hard coat film (6) is obtained. (Production of hard coat film (7)) The elastic modulus is 4.5 GPa and thick. ΙΟΟμπ! Polyethylene terephthalate i is applied to one side of the film to apply the above-prepared hard coating agent (3). [ After drying for 90 seconds, use an ultraviolet irradiation device in an air atmosphere. Deep-UV system, manufactured by Japan Co., Ltd. F450, lamp: i2〇w/cm, 200823255 Η valve) irradiated with ultraviolet light at a light amount of 〇5j/cm2 to form a hard coat layer of thickness. Next, by a corona treatment device The surface of the non-hard coating was surface-treated so that the surface tension was 55 dyne/cm, thereby obtaining a hard coat (7). (Measurement of the surface pencil hardness of the hard coat film) The hard coat obtained above was measured according to the regulations of JIS K5600-5-4 (1999 edition) using the pencil scratch tester of the coating film manufactured by the company. The surface pencil hardness of the films (1) to (7). Here, the measured surface pencil hardness is shown in Table 1. (Preparation of Adhesive Layer (1)) A release solution was applied to a release liner obtained by forming an anthrone compound release layer on one surface of a film having a thickness of 75 μη @ @聚 —, relative to 100 The mass of the big day is too scented with the outside, -&quot;, the Pseudo-Japan ink chemical company made the adhesive SPS1030B with h3 mass parts of the isocyanate I-type cross-linking agent (Japan polyamine 酉曰 酉曰 制造 制造 淫 淫Special £_45, solid content 45%)), at 9〇. Dry 90 heart clocks, the thickness after drying is formed! Called (5) the adhesive layer (1). (Preparation of Adhesive Layer (2)) For the surface of the film formed by the polyethylene glycolate having a thickness of 75 μm, a mixture of 1 r _ ... J is formed on the surface of the film formed by the ethylene glycol monoformate per 丨 M s The peeling lining obtained from the peeling layer of the mouth is coated with an adhesive solution (relative to the 100 quality 詈 、 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , a murmur-based cross-linking agent (Roenter L-45, manufactured by 曰本聚酯酯, 45% of the body composition), dried at 9 ° C for 90 seconds to form a dried ^ ^ ^ ^ ^ 3 0 μπι of the adhesive layer (2). (Preparation of Adhesive Layer (3)) 45 200823255 For the formation of an anthrone compound on one side of the film formed by the polyethylene glycol ester at a thickness of 75 μm, the formation of an anthraquinone compound peeling #her, a layer In the peeling lining, the adhesive solution was applied (in comparison with 100 parts by mass of the adhesive made by Toyo Ink Co., Ltd. BPS5762K with 6 mass parts of hardener Βχχ 5627).干燥 Drying for 90 seconds to form a dried adhesive layer (3) having a thickness of 1 μm. (Example 1) After the adhesive layer (1) was bonded to a corona-treated surface of a hard coat film (1) under a pressure of 4 kg/cm, it was aged at 40 ° C for 2 days to obtain a protective adhesive having a thickness of 93 μm. membrane. The obtained protective adhesive film was adhered to the glass plate, and the ultra-hardness tester Fei Xiyi HiQoc χ_ Yprog was used for the measurement of the micro hardness by the press-in depth of 1 μm and the press-in time i for 5 seconds. The result is 270 N/mm2. (Example 2) After the adhesive layer (1) was bonded to the corona-treated surface of the hard coat film (2) under a pressure of 4 kg/cm, it was aged at 40 ° C for 2 days to obtain a protective layer having a thickness of 93 μm. Adhesive film. (Example 3) After the adhesive layer (1) was bonded to the corona-treated surface of the hard coat film (3) under a pressure of 4 kS/cm, it was aged at 40 ° C for 2 days to obtain a thickness of 1 μμχ. Protect the adhesive film. (Example 4) After the adhesive layer (1) was adhered to the corona-treated surface of the hard coat film (4) under a pressure of 4 kg/cm, it was cured at 40 ° C for 2 days to obtain a protective adhesive having a thickness of 75 μm. membrane. 46 200823255 (Example 5) After the adhesive layer (1) was bonded to the corona-treated surface of the hard coat film (7) under a pressure of 4 kg/cm, after curing at 4 CTC for 2 days, a protective adhesion of 125 μm was obtained. membrane. The obtained protective adhesive film was adhered to a glass plate, and the minute hardness was measured in the same manner as above, and as a result, it was 3 10 N/mm 2 . (Comparative Example 1) After the adhesive layer (1) was bonded to the corona-treated surface of the hard coat film (5) under a pressure of 4 kg/cm, the protective adhesive layer having a thickness of 88 μm was obtained after 4 days of TC curing. (Comparative Example 2) The adhesive layer (2) was bonded to the corona-treated surface of the hard coat film (1) under a pressure of 4 kg/em, and then aged at 40 ° C for 2 days to obtain a thickness of 113 μm. (Adhesive Example 3) After the adhesive layer (1) was applied to the corona-treated surface of the hard coat film (6) under a pressure of 4 kg/cm, it was aged at 40 ° C for 2 days, and then obtained. Protective adhesive film having a thickness of 62 μm (Comparative Example 4) After applying the adhesive layer (3) under the pressure condition of 4 kg/cm on the corona-treated surface of the hard coat film (1), it was aged at 40 ° C for 2 days. After that, a protective adhesive film having a thickness of 113 μm was obtained. [Measurement of the surface hardness of the protective adhesive film] The protective adhesive film obtained in the above Examples and Comparative Examples was adhered to a glass plate according to JIS Κ 5600_5_4 (1999 edition). , using 47 200823255 • Co., Ltd. Co., Ltd. manufactured by the company, the film is scratched with a pencil scratch tester (manual) [Measurement of Viscoelastic Spectrum] The adhesive sheets obtained in the above Examples and Comparative Examples were laminated to a thickness of 2 mm to form a test piece, and the viscoelasticity was produced in the company of Ray-Europe, Inc.: Test Aares 2KSTD An Mengji secluded 7 working women's clothing with a diameter of 7.9mm parallel disc, the test piece is clamped into the parallel disc, with temperature dispersion method, frequency 1Hz, measurement, field range -3 (rc~1 (m: Conditional measurement (4) Spectral spectrum, read the storage elastic modulus G of W 80 C. [Observation of presence or absence of air bubbles] #Use manual observation of chemically strengthened diagonal angles of 2 inches and thickness o.8 mm under hanging temperature and normal pressure. The stone #Cristina IG3 was bonded to the adhesive sheets of the examples and comparative examples of the same size as test pieces.

The test piece was subjected to a 2 〇 冋 pressure cooker treatment under conditions of 5 〇t and 5 kgf/m 2 , and a 5 〇 φ 彳 镜 疋 在 在 在 在 在 共 共 共 共 共 共 共 共 共The number of bubbles at the time. Subsequently, it was placed in an environmental tester at 60 ° C, 90% RH. After placing it, the microscope was observed at a magnification of 5 times at the center of the sample and at five points in the four corners. Judgment is made as follows: • No air bubbles, X ·· There are air bubbles. [Adhesion] The adhesion test force of the adhesive tape of the present invention is determined by the following procedure in accordance with the test method of peeling adhesion of jIS_z〇237 (2〇〇〇). Under the conditions of ambient temperature 231 and humidity of 50%, the adhesive tape of the embodiment and the comparative example of 25 mm 48 200823255 was affixed to the glass plate by a 2 kg roller at a time of 1 hour. Using a Tensilon universal tensile tester (manufactured by Orientec, RTA100), stretching at a temperature of 300 mm/min under the same temperature and humidity conditions, peeling at 180 degrees, and measuring the adhesion force when peeling off the adhesive tape of 25 mm width (N ). Table Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Coating [μπιΐ PET substrate [μπιΐ adhesive layer [μπι] storage elastic tile] number (20 °C) [Pa] 8 8 15 15 15 3 8 2 8 75 75 75 50 100 75 75 50 75 2.5x10 5 2.5x10 5 2.5x10 5 2.5x10 5 10 30 2.5x10 5 2.5x10 5 2.5x10 5 2.5x10 5 2.0x10 5 Storage Elastic Modulus _ Number (80°C) [Pa^ 1.4x10 5 1.4x10 5 1.4x10 5 1.4x10 5 1.4x10 5 1.4x10 5 1.4x10 5 1.4x10 5 8.5x10 4

Ηκ -~^--~-i 丨I 丨I k The above table i shows that the protective adhesive film of the present invention can maintain a high surface hardness A and a suitable adhesion even if the total thickness is thin, and even a high temperature coat It is also difficult to generate bubbles under it. (Industrial Applicability) The protective adhesive film of the present invention, the thin glass ^ A 4 , for example, the protective degree of the sanitary glass panel for a portable electronic terminal, can be suitably used, and has a high surface The pencil is also hard to use. Or it can be used for the protection of various displays for 49.200823255. In addition, when the adhering object is glass or the like, cracking occurs: it can be effectively used as a scattering preventing film which prevents scattering when the adhering object is broken, and has a great industrial significance. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a portable electronic terminal of the present invention. 主要 [Main component symbol description] 1 protective adhesive film 2 glass plate 3 frame 4 LCD module 5 gap portion 50

Claims (1)

200823255 X. Patent application scope: 丨· A protective adhesive film attached to a hard coating film having a hard coating layer provided with an adhesive layer; characterized in that the elastic modulus of the film substrate The number is 3 to 7 GPa, and the thickness is 38 to 1 μm; the thickness of the hard coat layer is 5 to 25 μm; the hardness of the surface of the hard coat layer of the hard coat film is 3 Å or more; and the thickness of the adhesive layer is 5 ~2〇μπι; total thickness is 60~15〇μηι; The adhesive layer is 8 〇 in the dynamic viscoelastic spectrum at a frequency of 1 Hz and has a storage elastic modulus of 1.0 x 105 Pa or more. 2. The protective adhesive film of claim 1, wherein the adhesive layer has a storage elastic modulus of 1.0 1 1 05 Pa or more in the dynamic viscoelastic spectrum at a frequency of 1 Hz. 3_, for example, the protective adhesive film of the scope of the patent application, wherein the drawing speed of the glass plate is 18 时 at 3 〇〇mm/min. The peel adhesion is 4 to 12 N/25 mm. ^4. The protective adhesive film of claim 1, wherein the hard coat layer comprises a polymer (A) having a (meth) acrylonitrile group and 3 or more in j molecules ( a layer composed of a cured product of a reactive energy ray-curable resin composition of a polymethyl (meth) acrylate (B) having a methyl methacrylate group, the polymer having a (meth) acrylonitrile group (A) The (fluorenyl) acrylate-based polymer "i) having a reactive functional group in the side chain is reacted with an α, a polyunsaturated compound (a2) having a functional group reactive with the reactive functional group. 51 200823255 5 The protective adhesive film of claim 4, wherein the polymer (A) is a reaction product of a reaction of a glycidyl (meth)acrylate polymer with a, an unsaturated carboxylic acid. The protective adhesive film of claim 4, wherein the polymer (A) has a weight average molecular weight of 5, 〇〇〇~8 〇, 〇〇〇, and (f-based) acrylonitrile equivalent is 100 ~3〇〇g/eq. 7·Protection of Article 4 of the patent application scope The film, wherein the bismuth energy ray-curable resin composition contains a fluorinated alkyl group (meth) acrylate, and the fluorinated alkyl (meth) acrylate has a formula (1) a functional group having a fluorinated alkyl group at the end and two or more (meth) acrylonitrile groups, wherein the formula (1) is: R - OCC-Χ - Rf (1) Ο Η [In the formula (1), R is a hydrogen atom or an alkyl group having a carbon number of i to 4, and X is a stretching group which may have a hetero atom or a linking group represented by the following formula (2): Rf is fluorine The acyl group, the general formula (2) is: Ο II CH2-Y-CH-CO^CH^-- H2C-C-〇-(CH2)jrRf1 Ο (2) In the formula (2), 'Y is an oxygen atom Or a sulfur atom, the melon and n may be the same 'may be different, an integer of 1 to 4, and Rfi is a fluorinated alkyl group]. 8. The protective adhesive film according to item 7 of the patent application, wherein the content of fluorine atoms in the m molecules of the (?-)acrylic acid containing 52 V V200823255 alkylated alkyl group is 25% by weight or more, and the molecular weight is 500~ side. 9. If the patent application scope is 保护1, the protective adhesive film is 85, and the light* transmittance is 85% or more. A visceral panel comprising a protective adhesive film of any one of claims 1 to 9 and a laminated body of a glass plate having a thickness of 职. 11. A portable electronic terminal characterized in that, in a casing having a [CD module, the screen panel of the first application of the patent application is fixed to be spaced apart from the surface of the LCD module. Eleven, circle type, such as the next page 53