JP5446071B2 - Protective adhesive film, screen panel and portable electronic terminal - Google Patents

Description

  The present invention relates to a protective adhesive film for protecting a screen panel provided on the surface of a display device such as a liquid crystal panel or an EL display, a screen panel having a protective adhesive film, and a portable electronic terminal having the screen panel.

  With the demand for portable electronic terminals that are becoming smaller and shorter, image display devices (hereinafter referred to as display devices) are being made thinner. In order to prevent damage to a display device such as a liquid crystal, a protective screen panel (hereinafter referred to as a panel) is provided. In order to reduce the thickness, it is effective to reduce the thickness of the panel and reduce the gap between the display device and the panel.

  However, since conventional resin panels such as acrylic and polycarbonate are not rigid enough, pressing the panel part with a finger may cause deformation of the display device, resulting in poor display, or during long-term durability testing under wet heat conditions, etc. There arises a problem that the image display panel is partially pasted.

  Therefore, there is a demand for a highly rigid screen panel that replaces a conventional resin screen panel. For example, a glass plate panel has begun to be adopted. However, safety measures are required when a glass panel breaks. Therefore, the sticking of the protective adhesive film provided with the scattering prevention function on the surface of a panel is examined. As the protective adhesive film, Patent Document 1 discloses a hard coat film for polarizing plates in a liquid crystal display or for protecting various displays. Although the disclosed hard film uses a 188 μm PET film as the base film and exhibits a surface pencil hardness of 4H, the film thickness is thick and is not suitable for thinning purposes. In addition, when the same hard coat agent is provided on a thin base film, it has a high surface pencil hardness of 3H or the like if it has a pressure-sensitive adhesive layer. There was a problem that the adhesive layer was deformed and the surface pencil hardness as a panel was greatly reduced.

JP-A-2005-320522

  The problem to be solved by the present invention is to provide a protective adhesive film capable of maintaining a high surface hardness even when a thin panel is formed by laminating a glass plate or the like through an adhesive layer, Another object of the present invention is to provide a screen panel having both moderate elasticity and high surface hardness, and to provide a portable electronic terminal in which the panel surface is less likely to be damaged.

  In the present invention, a protective adhesive film in which an adhesive layer having a specific thickness is provided on a hard hard coat film in which a base material having a specific elastic modulus and a hard hard coat layer are combined at a specific thickness, Even when the pressure is applied locally to the surface of the protective adhesive film by impact or the like, even if it is thin, due to the presence of the adhesive layer The characteristics of the hard coat film in the absence of the pressure-sensitive adhesive layer can be satisfactorily expressed by appropriately relaxing the dent of the film.

  That is, the present invention is a protective adhesive film in which an adhesive layer is provided on a hard coat film comprising a film substrate having a hard coat layer, and the elastic modulus of the film substrate is 3 to 7 GPa and the thickness is 38 to 100 μm, the thickness of the hard coat layer is 5-25 μm, the pencil hardness of the hard coat layer surface of the hard coat film is 3H or more, the thickness of the pressure-sensitive adhesive layer is 5-20 μm, Provided is a protective adhesive film having a total thickness of 60 to 150 μm.

  For example, when the protective adhesive film of the present invention is used for protecting a thin glass panel of a portable electronic terminal, the protective adhesive film has a high surface pencil hardness, and therefore can be suitably used. Or it can use suitably for protection of various displays.

  Moreover, when a sticking target is what causes a crack of glass or the like, it is useful as a scattering prevention film for preventing scattering when the sticking target is cracked.

[Film substrate]
In the present invention, a film substrate having an elastic modulus of 3 to 7 GPa and a thickness of 38 to 100 μm is used. The protective adhesive film that protects the surface of the display body and the like is desired to have a thickness of at least 150 μm or less because of problems in appearance and peeling due to catching of the edge portion. For this reason, it is necessary for the base film to be a thin base, and from the viewpoint that lamination with other layers is required, it is necessary to set the base film to at least 100 μm or less. In this case, when the elastic modulus is less than 3 GPa, the film base material is likely to be deformed when the protective adhesive film is formed, and the decrease in surface hardness cannot be suppressed when the protective adhesive film is formed. Moreover, when it is 7 GPa or more, the film substrate becomes too hard and cannot follow a gently curved surface when the protective adhesive film is attached. Further, when the thickness is less than 38 μm, even if the thickness is within the above elastic modulus range, the film base material is likely to be deformed. Therefore, when the pressure-sensitive adhesive layer is provided, a decrease in surface hardness cannot be suppressed.

  Examples of the film substrate used in the present invention include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, and polyvinyl chloride film. , Polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide Film, fluorine resin film, nylon film, acrylic resin And the like can be given Irumu.

  In addition, for the purpose of improving the adhesion with the hard coat layer and the pressure-sensitive adhesive layer, surface roughening treatment such as sandblasting or solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone Surface treatment such as surface oxidation treatment such as ultraviolet irradiation treatment can be performed.

  In addition, an antistatic agent can be added as a blending material to impart an antistatic function. Nonionic polyoxyethylene alkyl ether, polyoxyethylene alkylphenol, polyoxyethylene alkylamine, polyoxyethylene alkylamide, fatty acid polyethylene glycol ester, fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, fatty acid glycerin ester, alkyl polyethyleneimine, etc. Can be mentioned. Examples of the cationic system include alkylamine salts, alkyl quaternary ammonium salts, and alkyl imidazoline derivatives. An acrylate compound having ethylene oxide as a skeleton can also be used. Polyaniline, polypyrrole, polythiophene, poly3,4-ethylenedioxythiophene, and derivatives thereof can be used as the conductive polymer. As the metal oxide, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), aluminum-doped zinc oxide, antimony suboxide, or the like can be used. In addition, an ion conduction type antistatic agent in which metal ions such as lithium ions are mixed can also be used.

[Hard coat layer]
The hard coat layer used in the present invention is not particularly limited as long as it has a hardness of 3H or more when laminated with the above-mentioned film base material, and those made of cured products of various hard coat agents can be used.

  As the hard coating agent, an active energy ray-curable resin composition can be suitably used. Among them, the reactive functional group and the (meth) acrylate polymer (a1) having a reactive functional group in the side chain are combined with the reactive functional group. A polymer (A) having a (meth) acryloyl group reacted with an α, β-unsaturated compound (a2) having a functional group capable of reaction, and three or more (meth) acryloyl groups in one molecule. The active energy ray-curable resin composition containing the polyfunctional (meth) acrylate (B) has a hard coat in which the resulting cured product is less likely to warp, and the cured product of the composition is a hard coat layer. Even when a pressure-sensitive adhesive layer is provided on the film, it is particularly suitable because the surface hardness hardly decreases. In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and the same applies to “(meth) acryloyl group” and “(meth) acrylic acid”.

  As the reactive functional group of the (meth) acrylate polymer (A1) having a reactive functional group in the side chain, a hydroxyl group, a carboxyl group, an epoxy group or the like is preferable. Moreover, as a functional group which the (alpha), (beta)-unsaturated compound (a2) which can react with these reactive functional groups has, an isocyanate group, a carboxyl group, an acid halide group, a hydroxyl group, an epoxy group etc. are preferable. The (meth) acrylate polymer (A1) having a reactive functional group in the side chain was reacted with an α, β-unsaturated compound (a2) having a functional group capable of reacting with the reactive functional group. The production method of the polymer (A) having a (meth) acryloyl group is not particularly limited, and can be produced by a conventionally known method. Examples thereof include the following production methods (1) to (3). It is done.

  Production Method (1) As the (meth) acrylate polymer (A1), using a (meth) acrylate polymer or copolymer having a hydroxyl group as a reactive functional group in the side chain, a part of the hydroxyl group or A method of introducing a (meth) acryloyl group by reacting (meth) acryloylethyl isocyanate, (meth) acrylic acid, (meth) acrylic acid chloride and the like as the α, β-unsaturated compound (a2).

  Production Method (2) As the (meth) acrylate polymer (A1), a (meth) acrylate polymer or copolymer having a carboxyl group as a reactive functional group in the side chain is used. In part or all, as the α, β-unsaturated compound (a2), an acrylate containing a hydroxyl group and a (meth) acryloyl group, or an acrylate having an epoxy group and a (meth) acryloyl group is reacted to form a (meth) acryloyl group How to introduce.

  Production Method (3) As the (meth) acrylate polymer (A1), a (meth) acrylate polymer or copolymer having an epoxy group as a reactive functional group in the side chain is used. A method in which (meth) acrylic acid or an acrylate having a carboxyl group and an acryloyl group is reacted as an α, β-unsaturated compound (a2) to a part or all of them to introduce a (meth) acryloyl group.

  Taking the production method (3) as an example, the production method of the polymer (A) will be described more specifically. In the production method (3), the polymer (A) can be easily obtained by reacting an (meth) acrylate polymer or copolymer having an epoxy group with an α, β-unsaturated carboxylic acid. . Here, the (meth) acrylate polymer having an epoxy group includes, for example, glycidyl (meth) acrylate and (meth) acrylate having an alicyclic epoxy group (for example, “CYCLOMER manufactured by Daicel Chemical Industries, Ltd.). M100 ”,“ CYCLOMER a200 ”), and (meth) acrylate having an epoxy group such as 4-hydroxybutyl acrylate glycidyl ether, and these are obtained by homopolymerization.

  In addition, the (meth) acrylate-based copolymer having an epoxy group is an α, which does not have a carboxyl group such as (meth) acrylate, styrene, vinyl acetate, acrylonitrile, in addition to the (meth) acrylate having the epoxy group. It can be obtained by copolymerizing two or more monomers using a β-unsaturated monomer as a raw material. When an α, β-unsaturated monomer having a carboxyl group is used instead of the α, β-unsaturated monomer having no carboxyl group, the copolymerization reaction with glycidyl (meth) acrylate is carried out. At this time, it is not preferable because a crosslinking reaction is caused to increase the viscosity and gelation.

  Examples of the α, β-unsaturated carboxylic acid that reacts with the (meth) acrylate-based polymer or copolymer having an epoxy group include (meth) acrylic acid, a compound having a carboxyl group and an acryloyl group (for example, Osaka Organic Chemical Co., Ltd. “Biscoat 2100”) and the like.

  The weight average molecular weight of the polymer (A) obtained by the above production method is preferably 5,000 to 80,000, more preferably 5,000 to 50,000, and still more preferably 8,000 to 35,000. When the weight average molecular weight is 5,000 or more, the effect of reducing curing shrinkage is large, and when it is 80,000 or less, the hardness is sufficiently high.

  The (meth) acryloyl group equivalent of the polymer (A) is preferably 100 to 300 g / eq, more preferably 200 to 300 g / eq. When the (meth) acryloyl group equivalent of the polymer (A) is within this range, curing shrinkage can be reduced and the hardness can be sufficiently increased.

  When the polymer (A) is produced by the above production methods (1) to (3), the polymer (A) is used so as to satisfy the weight average molecular weight and the (meth) acryloyl group equivalent. The kind of the polymer and polymer, the amount of use thereof, and the like may be appropriately selected.

  Examples of the polyfunctional (meth) acrylate (B) having three or more (meth) acryloyl groups in one molecule include trimethylolpropane tri (meth) acrylate and triethylene oxide-modified trimethylolpropane tri (meth). Acrylate, tripropylene oxide-modified glycerin tri (meth) acrylate, triethylene oxide-modified glycerin tri (meth) acrylate, triepichlorohydrin-modified glycerin tri (meth) acrylate, 1,3,5-triacroylhexahydro-s- Triazine, tris (acryloyloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetraethylene oxide modified pentaerythritol tetra ( ) Acrylate, ditrimethylolpropane tetra (meth) acrylate, diethylene oxide modified ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol pentaacrylate (for example, manufactured by Nippon Kayaku Co., Ltd.) “Kayarad D-310”), alkyl-modified dipentaerythritol tetraacrylate (for example, “Kayarad D-320” manufactured by Nippon Kayaku Co., Ltd.), ε-caprolactone-modified dipentaerythritol hexaacrylate (for example, manufactured by Nippon Kayaku Co., Ltd.) “Kayarad DPCA-20”), dipentaerythritol pentamethacrylate, dipentaerythritol hexa (meth) acrylate, hexaethylene oxide modified sorbitol Examples include ruhexa (meth) acrylate, hexakis (methacryloyloxyethyl) cyclotriphosphazene (for example, “PPZ” manufactured by Kyoeisha Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more.

  Among the polyfunctional (meth) acrylates (B), when pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, or dipentaerythritol hexaacrylate is used, the cured product of the composition is hard-coated. Even when an adhesive layer is provided on the hard coat film as a layer, the surface hardness is not easily lowered, which is particularly preferable.

  The blend ratio of the polymer (A) and the polyfunctional (meth) acrylate (B) is preferably in the range of (A) :( B) = 10: 90 to 90:10 on a mass basis, and (A) :( The range of B) = 20: 80 to 80:20 is more preferable, and the range of (A) :( B) = 30: 70 to 70:30 is more preferable. If the blend ratio of the polymer (A) and the polyfunctional (meth) acrylate (B) is within this range, the resulting cured product is unlikely to warp, and the cured product of the composition is a hard coat layer. Even when a hard coat film is provided with a pressure-sensitive adhesive layer, the surface hardness is hardly lowered, which is particularly suitable.

  In addition to the polymer (A) and the polyfunctional (meth) acrylate (B), a radical polymerizable monomer (C) can be blended with the active energy ray-curable resin composition. Examples of the radical polymerizable monomer (C) include N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylcarbazole, vinylpyridine, acrylamide, N, N-dimethyl (meth) acrylamide, and isobutoxymethyl (meth) acrylamide. , T-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, acryloylmorpholine, lauryl ( (Meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate DOO, ethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, methyl triethylene diglycol (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate.

  When the radically polymerizable monomer (C) is blended with the active energy ray-curable resin composition, the blending amount is the sum of the polymer (A) and the polyfunctional (meth) acrylate (B). 1-50 mass parts is preferable with respect to 100 mass parts, 1-30 mass parts is more preferable, and 1-10 mass parts is further more preferable.

  Further, as the polyfunctional (meth) acrylate (B) or the radical polymerizable monomer (C), a monomer having an acid group such as a carboxyl group, a phosphoric acid group or a sulfonic acid group, or a single monomer having an amino group It is preferable to use a monomer having an alkyl group, an alkoxysilyl group, or an alkoxy titanyl group, because the adhesion to the substrate can be increased. On the other hand, a monomer having a fluorocarbon chain, a dimethylsiloxane chain, or a hydrocarbon chain having 12 or more carbon atoms can improve the surface properties of the protective layer such as surface slipperiness, stain resistance, and fingerprint resistance. preferable. The addition amount of the monomer having a fluorocarbon chain, a dimethylsiloxane chain, and a hydrocarbon chain having 12 or more carbon atoms is preferably from 0.01 to 5 mass%, more preferably from 0.1 to 3 mass%.

  A monomer having a fluorocarbon chain is excellent in surface properties such as stain resistance and fingerprint resistance, but in particular, the following general formula (1)

〔式（１）中、Ｒは水素原子又は炭素数１〜４のアルキル基であり、Ｘはヘテロ原子を有していても良いアルキレン鎖、又は下記一般式（２）

[In Formula (1), R is a hydrogen atom or a C1-C4 alkyl group, X is the alkylene chain which may have a hetero atom, or following General formula (2).

｛式（２）中、Ｙは酸素原子又は硫黄原子であり、ｍとｎは同一でも異なっていても良い１〜４の整数であり、Ｒｆ^１はフッ素化アルキル基である。｝
で表される連結基であり、Ｒｆはフッ素化アルキル基である。〕
で表される末端にフッ素化アルキル基を有する官能基と、２個以上の（メタ）アクリロイル基とを有するフッ素化アルキル基含有（メタ）アクリレートが、表面性の向上に加え、表面硬度の向上にも寄与するため、特に好ましく使用できる。

{In Formula (2), Y is an oxygen atom or a sulfur atom, m and n are the same or different integers of 1 to 4, and Rf ¹ is a fluorinated alkyl group. }
Rf is a fluorinated alkyl group. ]
Fluorinated alkyl group-containing (meth) acrylate having a functional group having a fluorinated alkyl group at the terminal and two or more (meth) acryloyl groups, in addition to improving surface properties, improves surface hardness Can also be used particularly preferably.

In the structure represented by the general formula (1), since an alkylene chain or the like is interposed between the carbonyl carbon in the ester bond and the fluorinated alkyl group, there is little problem of deterioration due to hydrolysis, and the performance of the cured product is reduced. Excellent long-term stability. Further, since the fluorinated alkyl group in the structure is present at the end of the molecule, it is not taken in as a part of the network when crosslinked. Furthermore, it has a —CF ₃ group that greatly contributes to the ability to lower the surface tension. For this reason, for example, when used as a coating material, fluorine atoms can be effectively arranged on the surface, and surface characteristics derived from fluorine atoms can be efficiently expressed.

  Furthermore, it is essential that the fluorinated alkyl group-containing (meth) acrylate used in the present invention has two or more (meth) acryloyl groups. This is to have two or more crosslinking points in one molecule at the time of curing reaction, and is necessary for forming a strong three-dimensional network structure.

  Furthermore, although it is essential that the fluorine atom content in one molecule is 25% by weight or more, this is necessary to develop surface characteristics and optical characteristics derived from fluorine atoms. When a fluorine atom content of less than 25% by weight is used, the amount of fluorinated alkyl group-containing (meth) acrylate used may be increased in order to develop sufficient surface characteristics and optical characteristics, It is necessary to use a reactive compound having a high fluorine atom content and / or a non-reactive compound in combination, which is economically disadvantageous, and in order to develop optical properties, There arises a problem that a detailed blending ratio must be determined after sufficiently examining the solubility.

  Further, it is essential that the molecular weight of the (meth) acrylate is 500 to 4000. When the molecular weight is larger than 4000, the crosslinking density is lowered and the mechanical properties are insufficient, which is not preferable, and those having a molecular weight smaller than 500 are not preferable because fluorine atoms cannot be sufficiently introduced.

  By using a (meth) acrylate containing a fluorinated alkyl group that satisfies the above conditions, it exhibits excellent surface properties and optical properties of a cured product, which is a performance derived from fluorine atoms, and has a high crosslinking density and is more rigid. A three-dimensional network structure can be formed, the mechanical properties (mechanical strength) are improved, and as a result, a cured product having these performances can be obtained, and further, a cured product having excellent hydrolysis resistance Become.

  Among these, the fluorine atom content in one molecule of the fluorinated alkyl group-containing (meth) acrylate is particularly preferably 25% by weight or more, and the fluorine atom content is 30 to 65% by weight because of the excellent performance. % Is particularly preferred. Moreover, it is preferable that molecular weight is 500-4000, and it is especially preferable that it is 600-3500.

  Furthermore, the functional group and the two or more (meth) acryloyl groups are each independently 4 through an alkylene chain having 1 to 5 carbon atoms which may have the same or different oxygen atoms. The quaternary carbon, cyanurate ring or phosphoryl group bonded to a secondary carbon, cyanurate ring or phosphoryl group, and the functional group bonded via the alkylene chain, is the two or more (meth) acryloyl groups. It is a structure in which at least one of them is bonded via the alkylene chain, and when a three-dimensional network structure is formed, a quaternary carbon having a low degree of freedom and a cyanurate ring are connected to a portion connecting the crosslinking points. Alternatively, a phosphoryl group can be arranged, and the three-dimensional network structure itself can be made more rigid to express the mechanical properties of the cured product, and a fluorinated alkyl group can be arranged in the vicinity of the crosslinking point. Te, from the viewpoint that is to combine the mechanical and optical properties of the cured product. For the above reason, the alkylene chain is preferably short, and particularly preferably an alkylene chain having 1 to 3 carbon atoms or an oxyalkylene chain having 1 to 3 carbon atoms.

As X in the general formula (1), the following general formula (3)
_{- (CH 2) p -Z q} - (CH 2) r - (3)
[In Formula (3), Z is a hydrogen atom or a nitrogen atom, an oxygen atom, a sulfur atom, or —NR—SO ₂ — (R is a hydrogen atom, or a C 1-24 carbon atom having an alkyl group having 1 to 24 carbon atoms. P is an integer of 0 to 4, q is 0 or 1, r is an integer of 0 to 20, and 1 ≦ p + r ≦ 20. ]
Is preferable from the viewpoint of excellent hydrolysis resistance of the resulting cured product, and in particular, X in the general formula (1) is an alkylene chain represented by the general formula (3) [ However, Z is a hydrogen atom or a nitrogen atom, oxygen atom, sulfur atom, or —NR—SO ₂ — (R is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms) having a C 1-24 alkyl group. ), P is 1, q is 1, and r is an integer of 0 to 19. Or a linking group represented by the general formula (2) [wherein Rf ¹ is —C _n F _{2n + 1} (n is an integer of 1 to 20)]. And a compound in which Rf in the general formula (1) is the same as or different from Rf1 —C _n F _{2n + 1} (n is an integer of 1 to 20) can be produced by a Michael addition reaction described later. Therefore, it is suitable for industrial production, and since the fluorinated alkyl group is a perfluoroalkyl group, it is preferable from the viewpoint that performance derived from a fluorine atom can be effectively expressed. In addition, when a fluorinated alkyl group other than a perfluoroalkyl group is used, it has an effect of improving the compatibility with other components to be blended as necessary and further improving the translucency, etc. It is also effective when used in applications where the toughness and adhesion of the cured product are required, and the structure and type of the fluorinated alkyl group can be changed depending on the required level of performance and application. It is preferable to select.

Further, Z in the general formula (3) is a hydrogen atom or a nitrogen atom having a C 1-6 alkyl group, a sulfur atom, or —NR—SO ₂ — (R is a C 1-6 alkyl group. Or Y in the general formula (2) is a sulfur atom, the carbon number n of Rf ¹ is 4, 6 or 8, and the carbon of Rf in the general formula (1) When a compound having a number n of 4, 6, or 8 is used, it is most preferable because surface properties, optical properties, and mechanical properties are particularly excellent. In addition, R in the general formula (1) is preferably a hydrogen atom or a methyl group from the viewpoint of industrial availability of raw materials and production by a Michael addition reaction.

  Examples of the fluorinated alkyl group-containing (meth) acrylate used in the present invention include compounds represented by the following general formulas (I) to (X).

〔式（Ｉ）〜（ＩＩＩ）中、Ｒ^１は水酸基、炭素数１〜４の直鎖状のアルキル基、ＣＨ_２＝ＣＨＣＯ_２ＣＨ_２−、ＣＨ_２＝Ｃ（ＣＨ_３）ＣＯ_２ＣＨ_２−、又は炭素数１〜３のアルキロール基であり、Ｒ^２は（メタ）アクリロイル基であり、ｍとｎは同一でも異なっていても良い１〜４の整数であり、ｔは４、６、又は８であり、ｉは１又は２であり、ｊは２又は３であり、且つｉ＋ｊ＝４である。〕

[In the formulas (I) to (III), R ¹ is a hydroxyl group, a linear alkyl group having 1 to 4 carbon atoms, CH ₂ = CHCO ₂ CH _2- , CH ₂ = C (CH ₃ ) CO ₂ CH ₂ -Or an alkylol group having 1 to 3 carbon atoms, R ² is a (meth) acryloyl group, m and n are the same or different integers of 1 to 4, and t is 4, 6 Or 8, i is 1 or 2, j is 2 or 3, and i + j = 4. ]

〔式（ＩＶ）中、Ｒ^１、Ｒ^２は式（Ｉ）〜（ＩＩＩ）中のそれと同じであり、Ｒ^４は（メタ）アクリロイル基にＨＳ（ＣＨ_２）_２Ｃ_ｔＦ_２ｔ＋１又はＨＮ（Ｃ_３Ｈ_７）（ＣＨ_２）_２Ｃ_ｔＦ_２ｔ＋１（式中ｔは４、６又は８を示す。）がマイケル付加した基である。〕

Wherein ^{(IV), R 1, R} 2 is the same as that in formula (I) ~ (III), R 4 is (meth) _HS acryloyl group _{(CH 2) 2 C t F} 2t + 1 or HN ( C ₃ H ₇ ) (CH ₂ ) ₂ C _t F _{2t + 1} (wherein t represents 4, 6 or 8) is a group to which Michael was added. ]

〔式（Ｖ）中、Ｒ^２、Ｒ^４は式（Ｉ）〜（ＩＶ）中のそれと同じであり、ｍは１又は２であり、ｎは２又は３であり、且つｍ＋ｎ＝４である。〕

[In formula (V), R ² and R ⁴ are the same as those in formulas (I) to (IV), m is 1 or 2, n is 2 or 3, and m + n = 4. . ]

〔式（ＶＩ）中、Ｒ^２、Ｒ^４は式（Ｉ）〜（ＩＶ）中のそれと同じであり、ｐは１〜４の
整数であり、ｑは２〜５の整数であり、ｒは０〜３の整数であり、且つｐ＋ｑ＋ｒ＝６で
ある。〕

[In the formula (VI), R ² and R ⁴ are the same as those in the formulas (I) to (IV), p is an integer of 1 to 4, q is an integer of 2 to 5, and r is It is an integer of 0 to 3, and p + q + r = 6. ]

〔式（ＶＩＩ）〜（ＶＩＩＩ）中、Ｒ^２、Ｒ^４は式（Ｉ）〜（ＩＶ）中のそれと同じであり、ｗは１〜４の整数であり、ｗ’は２〜５の整数であり、且つｗ＋ｗ’＝６であり、ｙは１〜８の整数であり、ｙ’は２〜９の整数であり、且つｙ＋ｙ’＝１０である。〕

[In formulas (VII) to (VIII), R ² and R ⁴ are the same as those in formulas (I) to (IV), w is an integer of 1 to 4, and 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. ]

〔式（ＩＸ）中、Ｒ^２、Ｒ^４は式（Ｉ）〜（ＩＶ）中のそれと同じである。〕

[In formula (IX), R ² and R ⁴ are the same as those in formulas (I) to (IV). ]

〔式（Ｘ）中、Ｒ^２、Ｒ^４は式（Ｉ）〜（ＩＶ）中のそれと同じである。〕

[In formula (X), R ² and R ⁴ are the same as those in formulas (I) to (IV). ]

  Specific examples of the fluorinated alkyl group-containing (meth) acrylate include the following compounds. The following specific examples show the case of acrylate, and any acryloyl group in the formula can be changed to a methacryloyl group. Furthermore, the following specific examples describe only the hydrogen atom as R in the general formula (1), and any one of the hydrogen atoms in the methylene group bonded to the carbonyl carbon can be changed to a methyl group. is there.

  Although it does not specifically limit as a manufacturing method of the said fluorinated alkyl group containing (meth) acrylate, For example, it has a compound containing 3 or more (meth) acryloyl groups, a fluorinated alkyl group, and active hydrogen A method of synthesizing by a Michael addition reaction with a compound, an alkylcarboxylic acid having a fluorinated alkyl group, a polyhydric alcohol and (meth) acrylic acid as raw materials, a polymerization inhibitor such as hydroquinone is added, hydrochloric acid, Examples include a method of reacting for 3 to 10 hours in the presence of an acid catalyst such as sulfuric acid while removing water generated by a condensation reaction at 80 to 120 ° C.

  In particular, since the former production method using the Michael addition reaction is an addition reaction, there is no compound by-produced by the reaction, and it can be allowed to proceed under mild conditions as will be described later. Since it is possible to easily adjust the atomic content, the number of functional groups of the (meth) acryloyl group, etc., as a method for obtaining the fluorinated alkyl group-containing (meth) acrylate used in the fluorine-containing photocurable composition of the present invention It is preferable.

  In addition, the monomer having a dimethylsiloxane chain is excellent in surface slipperiness and the like, and as the monomer, for example, a dimethylsiloxane skeleton, via a spacer made of an alkylene group such as an ethylene group or a polypropylene group, An acrylate having a (meth) acryloyl group introduced therein can be preferably used. Examples of these acrylates include BYK-UV3500 and BYK-UV3570 manufactured by Big Chemie, Ebecryl 1360 manufactured by Daicel UCB Corporation, and the like.

  Furthermore, as a component other than the above (A) to (C), an addition reaction product of polyisocyanate (d1) and acrylate (d2) having one hydroxyl group and two or more (meth) acryloyl groups in one molecule. You may mix | blend the urethane acrylate (D) which is.

  Examples of the polyisocyanate (d1) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4 , 4'-diphenylmethane diisocyanate and other aromatic isocyanate compounds; dicyclohexylmethane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated methylenebisphenylene diisocyanate, 1,4-cyclohexane diisocyanate and other alicyclic hydrocarbons Compound having two bonded isocyanate groups (hereinafter abbreviated as alicyclic diisocyanate); trimethylene diisocyanate, hexamethylene diisocyanate Compounds having two isocyanate groups attached to aliphatic hydrocarbons over preparative like (hereinafter, referred to as aliphatic diisocyanates.) And the like. These polyisocyanates can be used alone or in combination of two or more.

  Of these polyisocyanates (d1), aliphatic diisocyanates or alicyclic diisocyanates are preferable, and among them, isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated methylene bisphenylene diisocyanate, and hexamethylene diisocyanate are preferable. In particular, norbornane diisocyanate is most preferable.

  Examples of the acrylate (d2) having one hydroxyl group and two or more (meth) acryloyl groups in one molecule used in the present invention include trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples include polyacrylates of polyhydric hydroxyl group-containing compounds such as pentaerythritol penta (meth) acrylate, adducts of these polyacrylates with ε-caprolactone, adducts of these polyacrylates with alkylene oxide, epoxy Examples include acrylates. These acrylates (d2) can be used alone or in combination of two or more.

  Of these acrylates (d2), acrylates having one hydroxyl group and 3 to 5 (meth) acryloyl groups in one molecule are preferable. Examples of such acrylates include pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like, and these are particularly preferable because a cured film having high hardness can be obtained.

The urethane acrylate (D) used in the present invention is obtained by subjecting two components of the polyisocyanate (d1) and the acrylate (d2) to an addition reaction. The ratio of the acrylate (d2) to 1 equivalent of the isocyanate in the polyisocyanate (d1) is usually preferably 0.1 to 50, more preferably 0.1 to 10, and preferably 0.9 to 1.2 as the hydroxyl equivalent. Is more preferable. Moreover, 30-150 degreeC is preferable and, as for the reaction temperature of the said polyisocyanate (d1) and the said acrylate (d2), 50-100 degreeC is more preferable. In addition, the end point of reaction can be confirmed by calculating | requiring an isocyanate group content rate by the loss | disappearance of the infrared absorption spectrum of 2250cm < ^-1 > which shows an isocyanate group, or the method as described in JISK7301-1995, for example.

  Further, in the above addition reaction, a catalyst can be used for the purpose of shortening the reaction time. Examples of the catalyst include basic catalysts (amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, phosphines such as tributylphosphine and triphenylphosphine) and acidic catalysts (copper naphthenate, naphthene). Metal alkoxides such as cobalt acid, zinc naphthenate, tributoxyaluminum, tetrabutoxytrititanium and tetrabutoxyzirconium, Lewis acids such as aluminum chloride, and tin compounds such as dibutyltin dilaurate and dibutyltin diacetate). Of these, acidic catalysts are preferred, and tin compounds are most preferred. The catalyst is usually added in an amount of 0.1 to 1 part by mass with respect to 100 parts by mass of the polyisocyanate. If necessary, a solvent such as toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or a radical polymerizable monomer having no site that reacts with isocyanate, for example, the above radical polymerizable Monomers (C) that do not have a hydroxyl group or amino group may be used as the solvent. These solvents and monomers can be used alone or in combination of two or more.

  The urethane acrylate (D) preferably has a molecular weight in the range of 500 to 1,500. When the molecular weight is within this range, a cured film having a sufficiently high hardness can be obtained and the curing shrinkage can be reduced, so that the curl of the hard coat film having this cured film can also be reduced.

  When the urethane acrylate (D) is blended with the active energy ray-curable resin composition, the blending amount is 100 parts by mass in total of the polymer (A) and the polyfunctional (meth) acrylate (B). On the other hand, 1-100 mass parts is preferable.

  In the present invention, when the active energy ray-curable resin composition is used as a hard coat agent, a cured product is obtained by irradiating active energy rays. The active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. In addition, when the resin composition is cured with ultraviolet rays, a photopolymerization initiator is added to the active energy ray-curable resin composition. If necessary, a photosensitizer is further added. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. There is no.

  When curing with ultraviolet rays, effective photopolymerization initiators can be broadly classified into intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy. 2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino- (4-thio Acetophenone compounds such as methylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone; benzoin compounds such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 4,6-trimethylbenzoyldiphenyl Acylphosphine oxide compounds such as sphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; benzyl, methylphenylglyoxyester, oligo 2-hydroxy-2-methyl-1- [4- (1 -Methylvinyl) phenyl] propanone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4 And compounds such as-(2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one.

  On the other hand, examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl 4-phenylbenzophenone, o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide. Benzophenone compounds such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4 A thioxanthone compound such as dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; an aminobenzophenone compound such as Michler's ketone and 4,4′-diethylaminobenzophenone; 2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, phenyl glyoxylic acid methyl ester, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl- And compounds such as a mixture of acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester.

  Further, the photosensitizer suitably used for the active energy ray-curable resin composition used in the present invention is not particularly limited, but examples thereof include amines such as aliphatic amines and aromatic amines, o-tolylthiourea. And the like, and sulfur compounds such as sodium diethyldithiophosphate, s-benzylisothiouronium-p-toluenesulfonate, and the like.

  The amount of these photopolymerization initiators and photosensitizers used is preferably 0.1 to 20% by weight, preferably 0.5 to 10%, based on 100 parts by weight of the resin component in the active energy ray-curable resin composition. The mass% is more preferable.

  Moreover, various additives may be mix | blended with the active energy ray hardening-type resin composition used for this invention as needed, and you may dilute with a solvent if desired. Examples of the additive include a polymerization inhibitor, an antioxidant, a leveling agent, an antifoaming agent, a coating surface improver (wetting property, slip property improving agent, etc.), a plasticizer, a colorant, and inorganic fine particles.

  Examples of the inorganic fine particles include metal oxides such as titanium oxide, silicon oxide, aluminum oxide, zinc oxide, calcium oxide, magnesium oxide, zirconium oxide, and tin oxide. The average particle size of the inorganic fine particles is 1 μm or less, preferably 300 nm or less, more preferably 100 nm or less.

  Moreover, in order to ensure the adhesiveness with respect to various film base materials etc. of a hard-coat layer, you may mix | blend tackifier resin (henceforth TF) suitably.

  For TF, resins such as modified rosin, polymerized rosin, phenolic resins such as phenolic resins and alkylphenolic resins, aromatic petroleum based resins such as coumarone indene, aliphatic hydrocarbons and terpene resins can be used. Those modified with carboxyl or hydroxyl can also be used.

  Solvents used for dilution include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol and isopropyl alcohol; esters such as ethyl acetate, butyl acetate and ethyl sorbacetate; methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone And ketones. These solvents may be used alone or in combination of two or more.

[Method for producing hard coat film]
The protective adhesive film of the present invention is obtained by applying the active energy ray-curable resin composition on a film substrate and curing it to form a hard coat layer to form a hard coat film, and then a hard coat layer of the film substrate. It can manufacture by forming an adhesive layer in the surface on the opposite side to the surface which has.

  Examples of the method for applying the active energy ray-curable resin composition to the film substrate include gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, transfer coating, dip coating, spinner coating, and wheeler coating. , Brush coating, silk screen solid coating, wire bar coating, flow coating, and the like. Also, printing methods such as offset printing and letterpress printing may be used. Among these, gravure coating, roll coating, comma coating, air knife coating, kiss coating, wire bar coating, and flow coating are preferable because a coating film having a more constant thickness can be obtained.

  When ultraviolet rays are used as a device for irradiating active energy rays, the light source is a low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, electrodeless lamp (fusion lamp), chemical lamp, black light. Lamps, mercury-xenon lamps, short arc lamps, helium / cadmium lasers, argon lasers, sunlight, LEDs and the like can be mentioned. In addition, when the active energy ray-curable resin composition used in the present invention is applied to a film substrate to form a cured film, a flashing xenon-flash lamp is used. This is preferable because the influence of heat can be reduced.

  The thickness of the hard coat layer used in the present invention is adjusted to a thickness of 5 to 25 μm so that the hard coat function is suitably exhibited even when a protective adhesive film having a total thickness of 150 μm or less is formed. Preferably it is 5-20 micrometers, More preferably, it is 5-10 micrometers. If the thickness is less than 5 μm, the surface pencil hardness decreases, and if it exceeds 25 μm, the adhesive coating becomes difficult due to curing shrinkage of the hard coat layer.

[Hard coat film]
The hard coat film used in the present invention has at least the above-mentioned film base material and a hard coat layer, and is laminated through a pressure-sensitive adhesive layer on a display portion of an image display device used as a mobile application. From the viewpoint of substantially exhibiting the effect of preventing scratches, the pencil hardness of the hard coat layer surface is at least 3H or higher, and preferably 4H or higher. If it is less than 3H, surface pencil hardness will fall, when a glass panel and the hard coat film of this invention are laminated | stacked through an adhesive layer.

  In addition, a thin primer layer may be provided on the surface of the film base so that the total thickness does not exceed 150 μm in order to improve the adhesion with the hard coat layer.

[Adhesive layer]
As the pressure-sensitive adhesive layer used in the present invention, a pressure-sensitive adhesive layer having a thickness of 5 to 20 μm is used. In the present invention, by setting the thickness of the pressure-sensitive adhesive layer to the thickness, sufficient adhesive strength with the object to be adhered can be expressed, and even when stress concentration occurs on the surface of the protective adhesive film, the protective adhesive Since the elasticity modulus of the whole film can be kept high, it is thought that the fall of the hardness of the hard-coat layer provided in the adhesive film surface can be suppressed.

  For the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer used in the present invention, known acrylic, rubber-based, and silicone-based pressure-sensitive resins can be used. Among them, an acrylic copolymer containing a repeating unit derived from an acrylate ester having an alkyl group having 2 to 14 carbon atoms as a repeating unit is preferable from the viewpoint of light resistance and heat resistance. Examples thereof include acrylic copolymers containing repeating units derived from n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, ethyl acrylate and the like.

  Furthermore, as a repeating unit, a repeating unit derived from an acrylic ester having a polar group such as a hydroxyl group, a carboxyl group, or an amino group in the side chain and other vinyl monomers is contained in the range of 0.01 to 15% by mass. Is preferred. The acrylic copolymer can be obtained by copolymerization by a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, an ultraviolet irradiation method, or an electron beam irradiation method. The average molecular weight of the acrylic copolymer is preferably 400,000 to 1,400,000, and more preferably 600,000 to 1,200,000.

  Furthermore, it is preferable to add a crosslinking agent in order to increase the cohesive strength of the pressure-sensitive adhesive. As a crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, a chelate type crosslinking agent etc. are mentioned, for example. The addition amount of the crosslinking agent is preferably adjusted so that the pressure-sensitive adhesive layer has a gel fraction of 25 to 80%. A more preferable gel fraction is 40 to 75%. Among these, 50 to 70% is most preferable. When the gel fraction is less than 25%, the surface pencil hardness when the protective adhesive film is attached to the panel is lowered. On the other hand, if the gel fraction exceeds 80%, the adhesiveness decreases. The gel fraction is expressed as a percentage with respect to the original mass by immersing the cured adhesive layer in toluene, measuring the mass after drying of the insoluble matter left after standing for 24 hours, and measuring the mass.

  Furthermore, in order to improve the adhesive strength of the pressure-sensitive adhesive layer, a tackifier resin may be added. The tackifier resin to be added to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape of the present invention is a rosin resin such as rosin or an esterified product of rosin; a terpene resin such as a diterpene polymer or an α-pinene-phenol copolymer; Petroleum resins such as (C5) and aromatic (C9); styrene resins, phenol resins, xylene resins, and the like. In order to reduce the b * value of the pressure-sensitive adhesive layer after standing at 100 ° C. for 14 days to 6 or less, there are few unsaturated double bonds, esterified products of hydrogenated rosin and disproportionated rosin, aliphatic and aromatic series It is preferable to add petroleum tree or the like to the adhesive layer.

  In order to achieve both adhesion and yellowing resistance, it is preferable to use a highly disproportionated rosin ester, a polymerized rosin ester, and a petroleum resin in combination.

  As addition amount of tackifying resin, when an adhesive resin is an acrylic copolymer, it is preferable to add 10-60 mass parts with respect to 100 mass parts of acrylic copolymers. When attaching importance to adhesiveness, it is most preferable to add 20 to 50 parts by mass. When the adhesive resin is a rubber-based resin, it is preferable to add 80 to 150 parts by mass of the tackifier resin to 100 parts by mass of the rubber-based resin. In general, when the adhesive resin is a silicone resin, no tackifying resin is added.

  In addition to the above, known and commonly used additives can be added to the adhesive. For example, in order to improve the adhesion to glass, a silane coupling agent can be added in the range of 0.001 to 0.005. In addition, plasticizers, softeners, fillers, pigments, flame retardants, and the like can be added.

  The pressure-sensitive adhesive layer can be formed on the film substrate by a method generally used for application of the pressure-sensitive adhesive sheet. The composition of the pressure-sensitive adhesive layer is directly applied to the base film and dried, or once applied on a separator (release sheet), dried, and then bonded to the base film.

The storage elastic modulus (20 ° C.) of the pressure-sensitive adhesive layer is preferably 1.0 × 10 ⁵ Pa or more, and more preferably 2.5 × 10 ⁵ Pa or more. If it is less than 1.0 × 10 ⁵ Pa, since the pressure-sensitive adhesive is soft, the surface hardness of the protective film is significantly reduced.

[Protective adhesive film]
The protective adhesive film of the present invention is a protective adhesive film in which an adhesive layer is provided on the hard coat film, and has a total thickness of 60 to 150 μm, preferably 80 to 120 μm.

  The protective film of the present invention conflicts with preventing damage and deformation at the time of stress concentration while being a very thin film of 150 μm or less by combining and adjusting the physical property values of the constituent members to a specific range. Both properties can be achieved. As a result, an excellent surface hardness that cannot be obtained by a conventional protective film can be realized without providing a special hard coat layer or a film substrate having extremely high hardness and rigidity. Furthermore, since the protective film of the present invention does not require the use of a hard coat layer or a film substrate having extremely high hardness or rigidity, even if it is applied to an object to be applied, peeling due to repulsion is unlikely to occur.

  The protective adhesive film of the present invention can achieve a high surface hardness even when applied to an object to be applied via an adhesive layer, and is preferably 2H or more, more preferably 3H or more when attached to a glass plate. Can be achieved. It can be suitably used as a protective film for thin glass panels of portable electronic terminals and protective films for various displays. Moreover, when a sticking target is what causes a crack of glass or the like, it is useful as a scattering prevention film for preventing scattering when the sticking target is cracked.

[Screen panel]
The screen panel of the present invention comprises a laminate of a glass plate and the protective adhesive film of the present invention. Since the screen panel is hard to be scratched on the surface layer, it can be usefully used for the image display part of various displays, and in particular, a laminate of a protective adhesive film having a surface hardness of 3H or more and a glass plate attached to the glass plate. The screen panel, which is a body, is particularly useful for various display applications having the screen panel on the surface of the image display unit because the damage to the glass plate is particularly reduced.

The glass plate is preferably a tempered glass plate. Examples of a method for strengthening the glass plate include a physical strengthening method and a chemical strengthening method. In particular, chemical strengthening methods include an ion exchange method and an air cooling strengthening method. Examples of the material of the glass plate include float glass, alkali glass, non-alkali glass, and tempered glass.
[Portable electronic devices]
The portable electronic terminal of the present invention has a configuration in which a screen panel, which is a laminate of the protective film of the present invention, is fixed to a housing having an LCD module with a gap from the LCD module surface (FIG. 1). . In this configuration, since there is a gap at the bottom of the screen panel, the screen panel on the surface of the image display unit may be bent when an impact or the like is applied to the surface. When the curvature occurs, stress concentrates on the concave portion and it is easy to be damaged, but even in such a case, the protective adhesive film of the present invention can suitably prevent the damage. For this reason, the protective adhesive film and screen panel of this invention can be used especially suitably for the portable electronic terminal of the said structure.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these.

(Synthesis Example 1)
<Synthesis of polymer (A1)>
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 250 parts by mass of glycidyl methacrylate (hereinafter referred to as “GMA”), 1.6 parts by mass of lauryl mercaptan, and methyl isobutyl ketone (hereinafter, “MIBK”). 1000 parts by mass and 7.5 parts by mass of 2,2′-azobisisobutyronitrile (hereinafter referred to as “AIBN”) were added and stirred at 90 ° C. over 1 hour while stirring under a nitrogen stream. The temperature was raised and reacted at 90 ° C. for 1 hour. Next, while stirring at 90 ° C., a mixed solution composed of 750 parts by mass of GMA, 4.4 parts by mass of lauryl mercaptan, and 22.5 parts by mass of AIBN was dropped over 2 hours, and then reacted at 100 ° C. for 3 hours. Thereafter, 10 parts by weight of AIBN was charged, and further reacted at 100 ° C. for 1 hour, then heated to around 120 ° C. and reacted for 2 hours. Cool to 60 ° C., replace the nitrogen introduction tube with an air introduction tube, add 507 parts by mass of acrylic acid (hereinafter referred to as “AA”), 2 parts by mass of p-methoxyphenol, and 5.4 parts by mass of triphenylphosphine. After mixing, the reaction solution was bubbled with air, heated to 110 ° C., and reacted for 8 hours. Thereafter, 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 added. Obtained. In addition, the weight average molecular weight of the obtained polymer (A1) was 11,000 (based on polystyrene conversion by GPC), and the (meth) acryloyl group equivalent was 300 g / eq.

(Synthesis Example 2)
<Synthesis of polymer (A2)>
In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 200 parts by mass of GMA, 50 parts by mass of n-butyl methacrylate (hereinafter referred to as “nBMA”), 1.8 parts by mass of lauryl mercaptan, “MIBK” 1000 parts by mass and 7.5 parts by mass of AIBN were charged, and the mixture was heated to 90 ° C. over 1 hour while being stirred under a nitrogen stream, and reacted at 90 ° C. for 1 hour. Next, while stirring at 90 ° C., a mixture of 600 parts by weight of GMA, 150 parts by weight of nBMA, 4.8 parts by weight of lauryl mercaptan, and 22.5 parts by weight of AIBN was added dropwise over 2 hours, and then reacted at 100 ° C. for 3 hours. It was. Thereafter, 10 parts by weight of AIBN was charged, and further reacted at 100 ° C. for 1 hour, then heated to around 120 ° C. and reacted for 2 hours. Cool to 60 ° C, replace the nitrogen inlet tube with an air inlet tube, add 406 parts by mass of AA, 2 parts by mass of p-methoxyphenol, and 5.4 parts by mass of triphenylphosphine, and then bubble the reaction solution with air. While raising the temperature to 110 ° C., the reaction was allowed to proceed for 8 hours. Thereafter, 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 (A2) (MIBK solution having a nonvolatile content of 50% by mass) was added. Obtained. In addition, the weight average molecular weight of the obtained polymer (A2) was 8,800 (in terms of polystyrene by GPC), and the (meth) acryloyl group equivalent was 240 g / eq.

(Synthesis Example 3)
<Synthesis of fluorinated alkyl group-containing acrylate (average number of added functional groups: 2)>
In a 200 ml reaction flask, 28.9 g (0.05 mol) of dipentaerythritol hexaacrylate (Dainippon Ink & Chemicals, Inc., LUMICURE DPA-600), 1.0 g of triethylamine, 20 g of methyl isobutyl ketone (MIBK) at room temperature. 48.2 g (0.1 mol) of perfluorooctylethyl mercaptan was added dropwise with stirring. After completion of the dropwise addition, the mixture was further stirred at 50 ° C. for 3 hours, and MIBK and triethylamine were distilled off under reduced pressure with an evaporator (bath temperature of 50 ° C. or lower) to obtain the fluorinated alkyl group-containing acrylate represented by the structural formula (xxi). 76.8 g of a product (A3) comprising a mixture containing a compound further containing a compound having an acryloyl group and perfluorooctylethyl mercaptan addition reaction position different from the structural formula (xxi) was obtained. The 1H-NMR spectrum peaks and integral values of the product supported the synthesis.
1H-NMR:
δ
2.20-2.90 (m, 16H),
3.30-3.50 (m, 4H),
4.10-4.40 (m, 12H),
5.84 (d, J = 10.2 Hz, 4H),
6.10 (dd, J = 10.2, 17.2 Hz, 4H),
6.42 (d, J = 17.2 Hz, 4H)

(Preparation of hard coating agent (1))
100 parts by mass of MIBK solution (non-volatile content: 50% by mass) of polymer (A1) synthesized in Synthesis Example 1, 50 parts by mass of pentaerythritol tetraacrylate (hereinafter referred to as “PETA”), silicon hexaacrylate (Daicel UCB) "Ebecryl 1360" manufactured by Co., Ltd .; hereinafter referred to as "SiA") and 1 part by mass, and 4 parts by mass of a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone; hereinafter referred to as "HCPK") are uniformly mixed. The hard coating agent (1) was obtained by diluting with ethyl acetate so that the nonvolatile content was 40% by mass.

(Preparation of hard coating agent (2))
After uniformly mixing 100 parts by weight of MIBK solution (non-volatile content 50% by weight) of polymer (A2) synthesized in Synthesis Example 2, 50 parts by weight of PETA, 1 part by weight of SiA, and 4 parts by weight of HCPK, the non-volatile content is 40% by weight. As a result, it was diluted with ethyl acetate to obtain a hard coating agent (2).

(Preparation of hard coating agent (3))
100 parts by mass of MIBK solution (non-volatile content: 50% by mass) of polymer (A1) synthesized in Synthesis Example 1, 50 parts by mass of pentaerythritol tetraacrylate (hereinafter referred to as “PETA”), A3 synthesized above (Synthesis Example) 3) 1 part by mass and 4 parts by mass of HCPK were uniformly mixed and then diluted with ethyl acetate so that the nonvolatile content was 40% by mass to obtain a hard coat agent (3).

(Preparation of hard coat film (1))
The hard coat agent (1) prepared above is applied to one side of a polyethylene terephthalate film having an elastic modulus of 4.5 GPa and a thickness of 75 μm, dried at 60 ° C. for 90 seconds, and then irradiated with an ultraviolet irradiation device (fusion UV) in an air atmosphere. Using an “F450” manufactured by Systems Japan Co., Ltd., a lamp: 120 W / cm, an H bulb, ultraviolet rays were irradiated at an irradiation light amount of 0.5 J / cm ² to form a hard coat layer having a thickness of 8 μm. Next, the non-hard-coated surface was surface-treated with a corona treatment device so as to have a surface tension of 55 dynes / cm to obtain a hard-coated film (1).

(Preparation of hard coat film (2))
A hard coat film (2) was obtained in the same manner except that the hard coat agent (2) prepared above was used instead of the hard coat agent (1) used in the production of the hard coat film (1). .

(Preparation of hard coat film (3))
The hard coat agent (1) prepared above is applied to one side of a polyethylene terephthalate film having an elastic modulus of 4.5 GPa and a thickness of 75 μm, dried at 60 ° C. for 90 seconds, and then irradiated with an ultraviolet irradiation device (fusion UV) in an air atmosphere. Using an “F450” manufactured by Systems Japan Co., Ltd., a lamp: 120 W / cm, an H bulb, ultraviolet rays were irradiated with an irradiation light amount of 0.5 J / cm ² to form a hard coat layer having a thickness of 15 μm. Next, the non-hard-coated surface was surface-treated with a corona treatment device so that the surface tension was 55 dynes / cm to obtain a hard-coated film (2).

(Preparation of hard coat film (4))
A hard coat agent (1) is applied to one side of a polyethylene terephthalate film having an elastic modulus of 4.5 GPa and a thickness of 50 μm, dried at 60 ° C. for 90 seconds, and then irradiated with an ultraviolet ray irradiation device (Fusion UV Systems Japan Co., Ltd.) in an air atmosphere. A hard coat layer having a thickness of 15 μm was formed by irradiating with ultraviolet light at an irradiation light amount of 0.5 J / cm ² using “F450” manufactured by company, lamp: 120 W / cm, H bulb). Next, the non-hard-coated surface was surface-treated with a corona treatment device so that the surface tension was 55 dynes / cm to obtain a hard-coated film (4).

(Preparation of hard coat film (5))
A hard coat agent (1) is applied to one side of a polyethylene terephthalate film with an elastic modulus of 4.5 GPa and a thickness of 75 μm, dried at 60 ° C. for 90 seconds, and then irradiated with an ultraviolet irradiation device (Fusion UV Systems Japan Co., Ltd.) in an air atmosphere. A hard coat layer having a thickness of 3 μm was formed by irradiating with ultraviolet light at an irradiation light amount of 0.5 J / cm ² using “F450” manufactured by company, lamp: 120 W / cm, H bulb). Next, the non-hard-coated surface was surface-treated with a corona treatment device so as to have a surface tension of 55 dynes / cm to obtain a hard-coated film (5).

(Preparation of hard coat film (6))
A non-hard coat treated surface of a hard coat film (surface pencil hardness 3H) manufactured by Toray Film Processing Co., Ltd. having a hard coat layer with a thickness of 2 μm on one surface of a polyethylene terephthalate film having an elastic modulus of 4.5 GPa and a thickness of 50 μm. Using a corona treatment device, surface treatment was performed so that the surface tension was 55 dynes / cm to obtain a hard coat film (6).

(Preparation of hard coat film (7))
The hard coating agent (3) prepared above is applied to one side of a polyethylene terephthalate film having an elastic modulus of 4.5 GPa and a thickness of 100 μm, dried at 60 ° C. for 90 seconds, and then irradiated with an ultraviolet irradiation device (fusion UV) in an air atmosphere. Using an “F450” manufactured by Systems Japan Co., Ltd., a lamp: 120 W / cm, an H bulb, ultraviolet rays were irradiated with an irradiation light amount of 0.5 J / cm ² to form a hard coat layer having a thickness of 15 μm. Next, the non-hard-coated surface was surface-treated with a corona treatment device so as to have a surface tension of 55 dynes / cm to obtain a hard-coated film (7).

(Measurement of surface pencil hardness of hard coat film)
The surface pencil hardness of the hard coat films (1) to (7) obtained above is measured according to JIS K 5600-5-4 (1999 edition) by Imoto Seisakusho Co., Ltd. (Manual method). The measured surface pencil hardness is shown in Table 1.

(Preparation of adhesive layer (1))
A release liner having a silicone compound release layer formed on one side of a 75 μm thick polyethylene terephthalate film was coated with Daiichi Ink Chemical Co., Ltd. adhesive SPS1030B and dried at 90 ° C. for 90 seconds. A 10 μm pressure-sensitive adhesive layer (1) was formed.

(Preparation of adhesive layer (2))
The adhesive liner SPS1030B made by Dainippon Ink & Chemicals Co., Ltd. was coated on a release liner having a silicone compound release layer formed on one side of a 75 μm thick polyethylene terephthalate film and dried at 90 ° C. for 90 seconds. A 30 μm pressure-sensitive adhesive layer (2) was formed.

Example 1
The pressure-sensitive adhesive layer (1) was bonded to the corona-treated surface of the hard coat film (1) with a pressure of 4 kg / cm, and after curing at 40 ° C. for 2 days, a protective pressure-sensitive adhesive film having a thickness of 93 μm was obtained.

(Example 2)
The pressure-sensitive adhesive layer (1) was bonded to the corona-treated surface of the hard coat film (2) under a pressure of 4 kg / cm, and after curing at 40 ° C. for 2 days, a protective adhesive film having a thickness of 93 μm was obtained.

(Example 3)
The pressure-sensitive adhesive layer (1) was bonded to the corona-treated surface of the hard coat film (3) under a pressure of 4 kg / cm, and after curing at 40 ° C. for 2 days, a protective pressure-sensitive adhesive film having a thickness of 100 μm was obtained.

Example 4
The pressure-sensitive adhesive layer (1) was bonded to the corona-treated surface of the hard coat film (4) with a pressure of 4 kg / cm, and after curing at 40 ° C. for 2 days, a protective pressure-sensitive adhesive film having a thickness of 75 μm was obtained.
(Example 5)
The pressure-sensitive adhesive layer (1) was bonded to the corona-treated surface of the hard coat film (7) with a pressure of 4 kg / cm, and after curing at 40 ° C. for 2 days, a protective pressure-sensitive adhesive film having a thickness of 125 μm was obtained.

(Comparative Example 1)
The pressure-sensitive adhesive layer (1) was bonded to the corona-treated surface of the hard coat film (5) under a pressure of 4 kg / cm, and after curing at 40 ° C. for 2 days, a protective adhesive film having a thickness of 88 μm was obtained.

(Comparative Example 2)
The pressure-sensitive adhesive layer (2) was bonded to the corona-treated surface of the hard coat film (1) under a pressure of 4 kg / cm, and after curing at 40 ° C. for 2 days, a protective pressure-sensitive adhesive film having a thickness of 113 μm was obtained.

(Comparative Example 3)
The pressure-sensitive adhesive layer (1) was bonded to the corona-treated surface of the hard coat film (6) with a pressure of 4 kg / cm, and after curing at 40 ° C. for 2 days, a protective adhesive film having a thickness of 63 μm was obtained.

(Measurement of surface pencil hardness of protective adhesive film)
The protective adhesive films obtained in the above examples and comparative examples are attached to a glass plate, and the surface pencil hardness is applied according to JIS K 5600-5-4 (1999 edition). It measured using the pencil scratch test machine (manual type) for membranes.

It is sectional drawing which shows an example of the portable electronic terminal of this invention.

Explanation of symbols

1: protective adhesive film 2: glass plate 3: housing 4: LCD module 5: gap

Claims (9)

A protective adhesive film in which an adhesive layer is provided on a hard coat film comprising a film base material having a hard coat layer,
The elastic modulus of the film base is 3 to 7 GPa, the thickness is 38 to 100 μm,
The hard coat layer has a thickness of 5 to 25 μm,
The pencil hardness of the hard coat layer surface of the hard coat film is 3H or more,
The pressure-sensitive adhesive layer has a thickness of 5 to 20 μm,
The α, β-unsaturated compound (a2) having a functional group capable of reacting with the reactive functional group in the (meth) acrylate polymer (a1) having a reactive functional group in the side chain of the hard coat layer Active energy ray curing containing a polymer (A) having a (meth) acryloyl group reacted with a polyfunctional (meth) acrylate (B) having three or more (meth) acryloyl groups in one molecule Is a layer made of a cured product of a mold resin composition,
The active energy ray-curable resin composition has the following general formula (1):

[In Formula (1), R is a hydrogen atom or a C1-C4 alkyl group, X is the alkylene chain which may have a hetero atom, or following General formula (2).

{In Formula (2), Y is an oxygen atom or a sulfur atom, and m and n may be the same or different.
An integer from 1 to 4, Rf ¹ is a fluorinated alkyl group. }
Rf is a fluorinated alkyl group. ]
Containing a fluorinated alkyl group-containing (meth) acrylate having a functional group having a fluorinated alkyl group at the terminal and two or more (meth) acryloyl groups, with a total thickness of 60 to A protective adhesive film characterized by having a thickness of 150 μm. The protective adhesive film according to claim 1, wherein the storage elastic modulus at 20 ° C. (1 Hz) in the dynamic viscoelastic spectrum of the adhesive layer is 1.0 × 10 ⁵ Pa or more. The protective adhesive film according to claim 1 , wherein the polymer (A) is a reaction product obtained by reacting a glycidyl (meth) acrylate polymer with an α, β-unsaturated carboxylic acid. The protective adhesive film according to claim 1 or 3 , wherein the polymer (A) has a weight average molecular weight of 5,000 to 80,000 and a (meth) acryloyl group equivalent of 100 to 300 g / eq. The protective adhesive film according to claim 1 , wherein the fluorinated alkyl group-containing (meth) acrylate has a fluorine atom content in one molecule of 25% by weight or more and a molecular weight of 500 to 4000. Protective adhesive film according to any one of claims 1 to fifth optical transmittance of 85% or more. Protective adhesive film according to any one of the thickness of the film substrate, according to claim 1 to 6 is 75 to 100. A screen panel comprising a laminate of the protective adhesive film according to any one of claims 1 to 7 and a glass plate having a thickness of 0.1 to 1 mm. A portable electronic terminal, wherein the screen panel according to claim 8 is fixed to a housing having an LCD module with a gap from the surface of the LCD module.

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