TWI445747B - Protective adhesive film, screen panel and portable electronic terminal - Google Patents

Description

Protective adhesive film, screen panel and portable electronic terminal

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, a screen panel having a protective adhesive film, and a portable electronic terminal having the screen panel.

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 deformed when the panel portion is pressed with a finger, resulting in poor display, or the panel may be subjected to long-term durability tests such as wet heat conditions. A problem occurs when a part is attached to the image display panel.

Therefore, a high-rigidity screen panel that replaces the conventional resin-made screen panel is being sought, for example, a glass panel is 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 protecting various displays. The disclosed hard coat film uses a 188 micron PET film for the underlayer film and exerts a surface pencil hardness of 4H. However, since the film thickness is thick, it is not suitable for the purpose of thinning. In addition, when the same hard coat agent is provided on a thin underlayer film, if it has a structure without an adhesive layer, it has a high surface pencil hardness such as 3H, but if it is laminated on the panel, if the adhesive layer is interposed, The adhesive layer is deformed, and there is a problem that the hardness of the surface of the panel is greatly reduced.

Further, when the image display device is made thinner, the protective adhesive film itself is required to be thinner. As a thin surface-protecting sheet, an adhesive sheet for surface protection for use in image paper such as photographs having scratch resistance and chemical resistance is disclosed (see Patent Document 2). However, the surface hardness of the adhesive sheet is insufficient, and further improvement is required in order to be suitable for an image display device. In addition, since the protective adhesive sheet is used as the outermost layer of the image display device, it is required to have excellent peeling resistance. However, when a soft adhesive is used to secure the adhesive force, the surface hardness is lowered and the hair is caused in a high-temperature and high-humidity environment. Bubble situation.

Patent Document 1: Japanese Patent Laid-Open No. 2005-320522, Patent Document 2: Japanese Patent Laid-Open No. 2003-96410

An object of the present invention is to provide a protective adhesive film which can maintain a high surface hardness even when a panel having a small thickness is formed by laminating a layer with an adhesive such as a glass plate, and is hard to be produced in a high-temperature and high-humidity environment. A foaming adhesive film is provided, and a screen panel is provided which combines thinness with appropriate elasticity and high surface hardness and is excellent in visibility, and provides a portable electronic terminal which is difficult to cause damage on the panel surface and is excellent in visibility.

In the present invention, even a protective adhesive film provided with a specific thickness of an adhesive layer is adhered to the adhesive layer by a hard hard coating film (a substrate having a specific elastic modulus and a hard hard coat layer combined with a specific thickness) When the pressure is applied to the surface of the adhesive film by impact or the like, the film is recessed, and even if it is a thin thickness, the film can be appropriately recessed due to the presence of the adhesive layer, and the film can be satisfactorily exerted. Hard film properties when there is no adhesive layer. Further, by adjusting the viscoelasticity of the adhesive layer, the above-mentioned excellent surface hardness can be maintained, and at the same time, a suitable adhesive force can be achieved, and generation of bubbles can be suppressed when adhered to the adhering object.

That is, the present invention provides a protective adhesive film which is provided on a hard coat film having a hard coat layer and is provided with an adhesive layer; wherein the film base material has a modulus of elasticity of 3~ 7GPa, the thickness is 38~100μm, the thickness of the hard coat layer is 5~25μm, the pencil hardness of the hard coating surface of the hard coating film is 3H or more, the thickness of the adhesive layer is 5-20μm, and the total thickness is 60 ~150μm.

When the protective adhesive film of the present invention is used for the protective use of a thin glass panel such as a portable electronic terminal, it can be suitably used because of its high surface pencil hardness. Or it can be suitably used for the protective use 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 which prevents scattering when the adhering object is broken.

[film substrate]

In the present invention, a film substrate having an elastic modulus of 3 to 7 GPa, a thickness of 38 to 100 μm, and a light transmittance of 85% or more is used. The protective adhesive film for protecting the surface of the display body or the like is preferably a thickness of at least 150 μm from the viewpoint of the appearance problem and the peeling problem caused by the hook damage at the edge portion. Therefore, the base film must be a thin base material, and it must be at least 100 μm or less from the viewpoint of laminating with other layers. At this time, if the modulus of elasticity is less than 3 GPa, the film substrate is likely to be deformed when the protective adhesive film is formed, and the reduction in surface hardness cannot be suppressed when the protective adhesive film is formed. On the other hand, when it is 7 GPa or more, the film base material is too hard, and it is impossible to follow the gentle curved surface when the adhesion of the adhesive film is protected. Further, in the case where the thickness is less than 38 μm, even if the film substrate is easily deformed in the above-described elastic modulus range, it is impossible to suppress a decrease in surface hardness when the pressure-sensitive adhesive layer is provided. Further, the light transmittance is preferably 85% or more, more preferably 90% or more.

Examples of the film substrate used in the present invention include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, and polypropylene film. , celluloid, cellulose diacetate film, cellulose triacetate film, cellulose acetate butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate film, Polystyrene film, polycarbonate film, polymethylpentene film, polyfluorene film, polyether ether ketone film, polyether ruthenium film, polyether phthalimide film, polyimine film, fluororesin film, nylon Film, acrylic resin film, and 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, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, or ozone treatment can be performed. . Surface treatment such as surface oxidation treatment such as ultraviolet irradiation treatment.

An antistatic agent may be added as another compounding material to impart an antistatic function. Nonionics include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol, polyoxyethylene alkylamine, polyoxyethylene alkyl decylamine, fatty acid polyethylene glycol ester, fatty acid sorbitan ester. Polyoxyethylene fatty acid sorbitan ester, fatty acid glyceride, alkyl polyethyleneimine, and the like. Examples of the cation include an alkylamine salt, an alkyl quaternary ammonium salt, and an alkyl imidazoline derivative. Further, an acrylate compound having 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, antimony doped tin oxide (ATO), tin doped indium oxide (ITO), aluminum doped zinc oxide, cerium oxide or the like can be used. In addition to this, an ion conductive antistatic agent in which metal ions such as lithium ions are mixed may be used.

[hard coating]

The hard coat layer used in the present invention may have a hard coat layer formed of a cured product of various hard coat agents as long as it has a hardness of 3H or more when laminated with the film base material.

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 methyl (meth) acrylate-based polyfunctional (meth) acrylate (B) having a reactive functional group in a side chain of a (meth) acrylonitrile-based polymer (A) A composition obtained by reacting a (meth) acrylate-based polymer (a1) with an α,β-unsaturated compound (a2) having a functional group reactive with the above-mentioned reactive functional group, because the obtained cured product 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, "(meth) acrylate" means one or both of methacrylate and acrylate, "(meth)acryl fluorenyl" and "(meth)acrylic acid" The same is true.

The reactive functional group of the (meth) acrylate-based polymer (a1) having a reactive functional group as a side chain is preferably a hydroxyl group, a carboxyl group, an epoxy group or the like. The functional group of the α,β-unsaturated compound (a2) which can react with the reactive functional group is preferably an isocyanate group, a carboxyl group, a halogenated fluorenyl group, a hydroxyl group or an epoxy group. Here, the reaction of the (meth) acrylate-based polymer (a1) having a reactive functional group in the side chain with 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) is not particularly limited, and it can be produced by a conventionally known method, and examples thereof include the following production methods (1) to (3).

Manufacturing method (1)

A (meth) acrylate-based polymer or copolymer having a reactive functional group hydroxy group in a side chain is used as the (meth) acrylate-based polymer (a1) to give (meth) acryloyl ethyl isocyanate ( A method in which an α,β-unsaturated compound (a2) is reacted with a part or all of the hydroxyl group as a α,β-unsaturated compound (a2) to introduce a (meth)acrylonyl group.

Manufacturing method (2)

A (meth) acrylate-based polymer or copolymer having a reactive functional group carboxyl group in its side chain is used as the above (meth) acrylate-based polymer (a1), and an acrylic acid having a hydroxyl group and a (meth) acrylonitrile group is used. An ester or an acrylate having an epoxy group and a (meth)acryloyl group 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)acrylonyl group.

Manufacturing method (3)

A (meth) acrylate-based polymer or copolymer having a reactive functional epoxy group in its side chain is used as the above (meth) acrylate-based polymer (a1), and (meth)acrylic acid or having a carboxyl group and propylene A thiol group acrylate is a method in which an α,β-unsaturated compound (a2) is reacted with a part or all of the epoxy group to introduce a (meth) acrylonitrile group.

The production method of the polymer (A) will be more specifically described by taking the above production method (3) as an example. In the production method (3), the polymer (A) can be easily obtained by reacting a (meth) acrylate-based polymer or copolymer having an epoxy group with an α,β-unsaturated carboxylic acid. Here, the (meth) acrylate-based polymer having an epoxy group can be obtained by using, for example, glycidyl (meth) acrylate, (meth) acrylate having an alicyclic epoxy group (for example, daicel chemical industry shares) An epoxy group-containing (meth) acrylate such as CYCLOMER M100, CYCLOMER a200) or 4-hydroxybutyl acrylate glycidyl ether manufactured by the company is used as a raw material, and these raw materials are separately polymerized.

Further, the (meth) acrylate-based copolymer having an epoxy group may be (meth) acrylate, styrene, or acetic acid in addition to the above-mentioned (meth) acrylate having an epoxy group. An α,β-unsaturated monomer having no carboxyl group such as vinyl ester or acrylonitrile is obtained as a raw material and copolymerized with two or more kinds of monomers. Here, if an α,β-unsaturated monomer having a carboxyl group is used in place of the above α,β-unsaturated monomer having no carboxyl group, it is produced when copolymerized with glycidyl (meth)acrylate. The cross-linking reaction causes high viscosity or gelation, which is not preferable. The α,β-unsaturated carboxylic acid to be reacted with the above-mentioned epoxy group-containing (meth) acrylate-based polymer or copolymer may, for example, be (meth)acrylic acid, a compound having a carboxyl group and an acryloyl group (for example) Osaka Organic Chemical Co., Ltd. manufactures Biscott 2100).

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

Further, the (meth)acryl oxime equivalent of the polymer (A) is preferably from 100 to 300 g/eq, more preferably from 200 to 300 g/eq. When the (meth)acrylonitrile group equivalent of the polymer (A) is in this range, the hardening shrinkage can be reduced and the hardness can be sufficiently high.

When the polymer (A) is produced by the above production methods (1) to (3), in order to satisfy the weight average molecular weight and the (meth) acrylonitrile equivalent of the above polymer (A), the monomers used and the monomers used may be appropriately selected. The type of the polymer, the amount of the polymer used, and the like.

The polyfunctional (meth) acrylate (B) having three or more (meth) acrylonitrile groups in one molecule may, for example, be trimethylolpropane tri(meth) acrylate or tricyclic ring. Oxygen ethane modified trimethylolpropane tri(meth) acrylate, tripropylene oxide modified glycerol tri(meth) acrylate, triethylene oxide modified glycerol tri(meth) acrylate, three Epichlorohydrin modified glycerol tris(meth)acrylate, 1,3,5-tripropylene decyl hexahydro-s-triazine, tris(propylene decyloxyethyl)isocyanate, pentaerythritol tris Acrylate, pentaerythritol tetra(meth)acrylate, tetraethylene oxide modified pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, diethylene oxide Di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, alkyl-modified dipentaerythritol pentaacrylate (for example, Kayado D-made by Nippon Kayaku Co., Ltd.) 310"), alkyl modified dipentaerythritol tetraacrylate (for example, "Kayadora D-320" manufactured by Nippon Kayaku Co., Ltd.), ε-caprolactone modification Dipentaerythritol hexaacrylate (for example, "Kayadora DPCA-20" manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol pentamethyl acrylate, dipentaerythritol hexa(meth) acrylate, hexaethylene oxide Lithium sorbitol hexa(meth) acrylate, hexa(methacryloxyethyl)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.

Further, in the above polyfunctional (meth) acrylate (B), if pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate is used, an adhesive layer is provided to the composition. When the cured product is used as a hard coat film of a hard coat layer, the surface hardness is also hard to be lowered, so that it is particularly suitable.

The compounding ratio of the above polymer (A) and the polyfunctional (meth) acrylate (B) is preferably in the range of (A): (B) = 10: 90 to 90: 10, more preferably (A). ): (B) = 20: 80 to 80: 20, and further preferably (A): (B) = 30: 70 to 70: 30. When the compounding ratio of the above polymer (A) and the polyfunctional (meth) acrylate (B) is in this range, the obtained cured product is hard to be warped, and the adhesive layer is provided in the hardening of 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, a radical polymerizable monomer (C) may be blended in addition to the above polymer (A) and polyfunctional (meth) acrylate (B). Examples of the radical polymerizable monomer (C) include N-vinyl caprolactam, N-vinylpyrrolidone, N-vinylcarbazole, vinylpyridine, acrylamide, N,N-di Methyl (meth) acrylamide, isobutoxymethyl (meth) acrylamide, trioctyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylamine Ethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, acryloyl morpholine, laurel (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tetrahydrogen Mercapto (meth) acrylate, ethylene diethylene glycol (meth) acrylate, butoxy ethyl (meth) acrylate, methyl glycol ( Methyl) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like.

When the radical polymerizable monomer (C) is blended in the active energy ray-curable resin composition, the amount thereof is 100% based on the total of the polymer (A) and the polyfunctional (meth) acrylate (B). The mass part is preferably from 1 to 50 parts by mass, more preferably from 1 to 30 parts by mass, still more preferably from 1 to 10 parts by mass.

In addition, as the polyfunctional (meth) acrylate (B) or the radical polymerizable monomer (C), if a monomer having an acid group such as a carboxyl group, a phosphoric acid group or a sulfonic acid group is used, a monomer having an amine group is used. A monomer having an alkoxycarbenyl group or an alkoxytitanyl group is preferred because it can improve adhesion to a substrate. On the other hand, a monomer having a fluorocarbon chain, a dimethyl siloxane chain, or a hydrocarbon chain having 12 or more carbon atoms can improve the surface properties such as surface smoothness, stain resistance, and fingerprint adhesion of the protective layer. Preferably. The amount of the monomer having a fluorocarbon chain, a dimethyl siloxane chain, and a hydrocarbon chain having 12 or more carbon atoms is preferably 0.01 to 5% by mass, and more preferably 0.1 to 3% by mass.

The monomer having a fluorocarbon chain is excellent in surface properties such as stain resistance and fingerprint adhesion resistance, and particularly a fluorinated alkyl (meth) acrylate having an end represented by the following formula (1). The functional group of the fluorinated alkyl group and the two or more (meth) acrylonitrile groups, in addition to improving the surface properties, contribute to the improvement of the surface hardness, and therefore are particularly useful. The general formula (1) is: In the formula (1), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is an alkylene chain which may have a hetero atom or a linking group represented by the following formula (2), and Rf is a fluorine atom. The alkyl group, the formula (2) is: In the formula (2), Y is an oxygen atom or a sulfur atom, and m and n may be the same or different and may be an integer of 1 to 4, and Rf ¹ is a fluorinated alkyl group. }]

In the structure represented by the above formula (1), since an alkyl chain or the like exists between the carbonyl carbon and the fluorinated alkyl group in the ester bond, the problem of deterioration due to hydrolysis is small, and the long-term stability of the cured product property is excellent. Also, since the fluorinated alkyl group in the structure exists at the end of the molecule, it is not pulled in as a part of the mesh at the time of crosslinking. Further, it has a -CF ₃ group which contributes greatly to the reduction of surface tension. Therefore, for example, when used as a coating material, fluorine atoms can be efficiently disposed on the surface thereof, so that surface characteristics derived from fluorine atoms can be effectively exhibited.

Further, the (fluorenated alkyl group-containing (meth) acrylate used in the present invention must have two or more (meth) acrylonitrile groups. It has a crosslinking point at the time of two or more hardening reactions in one molecule, and is necessary for forming a strong 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 the fluorine atom are easily exhibited, which is preferable. When the fluorine atom content is 25% by weight or more, in order to exhibit surface characteristics and optical properties, the amount of the (fluorenated alkyl group-containing (meth) acrylate can be reduced, and other fluorine atom content ratios are not used in combination. The reactive compound and/or the non-reactive compound can exhibit sufficient characteristics, and sufficient compatibility can be obtained, and appropriate optical characteristics can be easily obtained.

Further, the molecular weight of the (meth) acrylate is preferably from 500 to 4,000. 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, it is possible to form a three-dimensionally high-strength and more rigid three-dimensional density while exhibiting excellent surface properties and optical properties from a fluorine atom. The mesh structure and the mechanical properties (mechanical strength) are improved, and as a result, a cured product having both of these properties can be obtained, and a cured product excellent in hydrolysis resistance can be formed.

In particular, the fluorine atom content in one molecule of the (fluorenated alkyl group-containing (meth) acrylate is preferably 25% by weight or more, and the fluorine atom content is particularly preferably 30. ~65% by weight. Further, the molecular weight is preferably from 500 to 4,000, particularly preferably from 600 to 3,500.

Further, the functional group and the two or more (meth)acrylonyl groups are independently bonded to the fourth-order carbon through the same or different alkylene chain having 1 to 5 carbon atoms which may have an oxygen atom. a cyanurate ring or a phosphonium group, and the above alkyl group is passed through the above-mentioned alkyl chain, through the above-mentioned functional group through the 4-stage carbon, cyanurate ring or phosphonium group to which the above alkyl chain is bonded A structure in which at least one of the above two or more (meth) acrylonitrile groups is bonded, and when a three-dimensional network structure is formed, four stages of carbon and three having a low degree of freedom can be disposed in a portion where the crosslinking points are connected to each other. a polycyanate ring or a phosphonium group, and the three-dimensional network structure itself becomes more rigid, exhibiting the mechanical properties of the cured product, and at the same time, by arranging a fluorinated alkyl group near the crosslinking point, the mechanical properties of the cured product can be combined And optical characteristics are therefore preferred. In view of the above reasons, the alkylene chain is preferably short, and particularly preferably an alkylene chain having 1 to 3 carbon atoms or an alkyloxy chain having 1 to 3 carbon atoms.

The X in the above formula (1) is preferably an alkylene chain represented by the following formula (3), -(CH ₂ ) _p -Z, from the viewpoint of the excellent hydrolysis resistance of the obtained cured product. _q -(CH ₂ ) _r - (3) [In the formula (3), Z is a nitrogen atom having a hydrogen atom or a C 1-24 alkyl group, an oxygen atom, a sulfur atom, or -NR-SO ₂ - ( R is a hydrogen atom or 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. ]

In particular, X in the above formula (1) is an alkyl group represented by the above formula (3) [wherein Z is a nitrogen atom having a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, an oxygen atom, sulfur An atom, or -NR-SO ₂ - (R is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms), p is 1, q is 1, r is an integer of 0 to 19, or is represented by the above formula (2) linking group represented by [wherein, Rf ¹ is a -C _n F _{2n + 1 (n} is an integer of 1 to 20)], and the formula an Rf (1) in the range of Rf ¹ are the same or different from -C _n F _{2n + 1} ( A compound in which n is an integer of 1 to 20) is suitable for industrial production from the viewpoint of production by a Michael addition reaction to be described later, and is effective because the fluorinated alkyl group is a perfluoroalkyl group. It is also preferable from the viewpoint of exerting the performance derived from a fluorine atom. In addition, when a fluorinated alkyl group other than a perfluoroalkyl group is used, the compatibility with other components described later is increased as needed, and the effect of improving light transmittance and the like is further enhanced, and the flexibility of the cured product can be effectively used. For the purpose of use and adhesion, 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 in the above formula (3) is a nitrogen atom having a hydrogen atom or a C1-6 alkyl group, a sulfur atom, or -NR-SO ₂ - (R is an alkane having 1 to 6 carbon atoms) Or the Y in the above formula (2) is a sulfur atom, the number of carbon atoms of Rf ¹ is 4, 6 or 8, and the number of carbon atoms of Rf in the above formula (1) is 4, 6 When it is a compound of 8 or more, it is excellent because it is especially excellent in surface characteristics, optical characteristics, and mechanical characteristics. Further, R in the above formula (1) is preferably a hydrogen atom or a methyl group from the viewpoint of ease of industrial availability of the raw material and production by a Michael addition reaction.

The (fluorinated alkyl group-containing (meth) acrylate used in the present invention is, for example, a compound represented by the following general formulae (I) to (X).

[In the formulae (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 alkanol group having 1 to 3 carbon atoms, R ² is a (meth) acrylonitrile group, m and n may be the same or different, and may be an integer 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. ] [In the formula (IV), R ¹ and R ² are the same as those in the formulae (I) to (III), and R ⁴ is HS(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) a group in which Michael is added to a (meth)acrylinyl group. ] [In the formula (V), R ² and R ⁴ are the same as those in the formulae (I) to (IV), m is 1 or 2, n is 2 or 3, and m + n = 4. ] [In the formula (VI), R ² and R ⁴ are the same as those in the formulae (I) to (IV), p is an integer of 1 to 4, q is an integer of 2 to 5, and r is an integer of 0 to 3, and p+q+r=6. ] [In the formulae (VII) to (VIII), R ² and R ⁴ 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. ] [In the formula (IX), R ² and R ⁴ are the same as those in the formulae (I) to (IV). ] [In the formula (X), R ² and R ⁴ 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. In the case where the following specific examples are all acrylates, the propylene fluorenyl group in the formula may be changed to a methacryl fluorenyl 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 methylene group bonded to the carbonyl carbon may be changed to a methyl group.

The method for producing the fluorinated alkyl group-containing (meth) acrylate is not particularly limited, and examples thereof include a compound containing three or more (meth) acryl fluorenyl groups and having a fluorinated alkyl group and an active hydrogen group. The compound is subjected to a Michael addition reaction to synthesize a method, or an alkyl carboxylic acid having a fluorinated alkyl group, a polyhydric alcohol, and a (meth)acrylic acid is used as a raw material, a polymerization inhibitor such as hydroquinone is added, and an acid contact such as hydrochloric acid or sulfuric acid is used. In the presence of a medium, a condensation reaction is carried out at 80 to 120 ° C, and a method of reacting for 3 to 10 hours while removing moisture generated by the reaction is carried out.

In particular, the above-mentioned production method using the Michael addition reaction, since it is an addition reaction, does not have a by-product formed with the reaction, and can be carried out under mild conditions as described later, and can easily adjust the fluorine atom content in the molecule. Since the ratio is the number of functional groups of the (meth) acrylonitrile group, etc., it is preferable as a method of obtaining the fluorinated alkyl (meth) acrylate used in the fluorinated photocurable composition of the present invention.

Further, the monomer having a dimethyl methoxyalkylene chain is excellent in surface smoothness and the like, and as the monomer, for example, a dimethyl methoxy oxane skeleton is allowed to pass through an alkyl group such as an ethyl group or a propyl group. The (meth)acryl fluorenyl acrylate or the like is introduced into the spacer formed. The acrylates are BYK-UV3500 and BYK-UV3570, diacel manufactured by Byk-chemie. Ebecryl1360 manufactured by UCBUCB Co., Ltd., etc.

Further, in the active energy ray-curable resin composition, an amine ester acrylate (D) may be blended as a component other than the above (A) to (C), and the component (D) is a polyisocyanate (d1) and An addition reaction product of an acrylate (d2) having one hydroxyl group and two or more (meth) acrylonitrile groups in one molecule.

Examples of the polyisocyanate (d1) include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 4,4'-diphenyl diisocyanate, and 1,5-. An aromatic isocyanate compound such as naphthalene diisocyanate or 4,4'-diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylene diisocyanate, hydrogenation a compound having two isocyanate groups bonded to an alicyclic hydrocarbon such as isopropylidene diisocyanate or 1,4-cyclohexane diisocyanate (hereinafter referred to simply as an alicyclic diisocyanate), trimethylene di A compound having two isocyanate groups bonded to an aliphatic hydrocarbon such as an isocyanate or hexamethylene diisocyanate (hereinafter simply referred to as an aliphatic diisocyanate). These polyisocyanates may be used singly or in combination of two or more.

Further, among the polyisocyanates (d1), aliphatic diisocyanates or alicyclic diisocyanates are preferred, and isophorone diisocyanate, norbornane diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated hydrogen are preferred. Methyl diphenylene diisocyanate and hexamethylene diisocyanate. Most preferred is norbornane diisocyanate.

The acrylate (d2) having one hydroxyl group and two or more (meth) acrylonitrile groups in one molecule used in the present invention may, for example, be trimethylolpropane di(meth)acrylate. And polyacrylates of a compound containing a polyvalent hydroxyl group such as pentaerythritol tri(meth)acrylate or dipentaerythritol penta(meth)acrylate, and addition of such polyacrylates and ε-caprolactone And an adduct of such polyacrylates and alkylene oxides, epoxy acrylates, and the like. These acrylates (d2) may be used alone or in combination of two or more.

Among the acrylates (d2), an acrylate having one hydroxyl group and three to five (meth) acrylonitrile groups in one molecule is preferred. Examples of such an acrylate include pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and these are particularly preferable because a hardened film having a high hardness can be obtained.

The amine ester acrylate (D) used in the present invention is obtained by subjecting the above-mentioned polyisocyanate (d1) and the above acrylate (d2) to an addition reaction. The ratio of the hydroxyl equivalent of the acrylate (d2) to the equivalent of one equivalent of the isocyanate in the polyisocyanate (d1) is usually preferably from 0.1 to 50, more preferably from 0.1 to 10, still more preferably from 0.9 to 1.2. Further, the reaction temperature of the above polyisocyanate (d1) and the above acrylate (d2) is preferably from 30 to 150 ° C, more preferably from 50 to 100 ° C. Here, the end point of the reaction can be confirmed by, for example, the disappearance of the infrared absorption spectrum of 2250 cm ^-1 of the isocyanate group or the method of the method described in JIS K 7301-1995.

Further, in the above addition reaction, a catalyst can be used for the purpose of shortening the reaction time. Examples of the catalyst include an alkaline catalyst (an amine such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine or ammonia, a phosphine such as tributylphosphine or triphenylphosphine), and an acidic touch. a metal alkoxide such as copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, tetrabutoxytrititanium or tetrabutoxyzirconium, Lewis acid such as aluminum chloride, dibutyltin a tin compound such as dilaurate or dibutyltin diacetate). Among them, an acidic catalyst is preferred, and a tin compound is preferred. 0.1 to 1 part by mass of the catalyst is usually added to 100 parts by mass of the polyisocyanate. A solvent such as toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone or a radical polymerizable monomer having no reaction site with isocyanate may be used as needed. For example, a monomer having no hydroxyl group or an amine group in the radical polymerizable monomer (C) described above is used as a solvent. These solvents and monomers may be used singly or in combination of two or more.

The molecular weight of the above amine ester acrylate (D) is preferably in the range of 500 to 1,500. When the molecular weight is in this range, since a hardened film having a sufficiently high hardness can be obtained, the hardening shrinkage is reduced, so that the curl of the hard coat film having the cured film can be reduced.

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 100% by mass based on the total of the above polymer (A) and polyfunctional (meth) acrylate (B). The portion is preferably from 1 to 100 parts by mass.

In the present invention, when the active energy ray-curable resin composition described above is used as a hard coating agent, a cured product 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 an electron beam, an α-ray, a β-ray, or a γ-ray is used, it is rapidly hardened without using a photopolymerization initiator and a photosensitizer, and 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. The intramolecular splitting type photopolymerization initiator may, for example, be diethoxyethyl benzene, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, or -(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholinyl-(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-( An acetophenone compound such as 4-morpholinylphenyl)butanone, a benzoin compound such as benzoin, benzoin methyl ether or benzoin isopropyl ether, 2,4,6-trimethyl a mercaptophosphine oxide compound such as benzylidene-based diphenylphosphine oxide or bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, benzophenone, methylbenzene Glyoxylate, oligo-2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone, 1-[4-(2-hydroxyethoxy)- Phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropenyl)-benzyl] -phenyl} a compound such as -2-methyl-propan-1-one.

On the other hand, examples of the dehydrogenation type photopolymerization initiator include benzophenone, methyl phthalyl benzoate-4-phenyl benzophenone, and 4,4'-dichlorobenzophenone. , hydroxybenzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide, benzophenone acrylate, 3,3',4,4'-tetra (t-butylperoxycarbonyl) a benzophenone compound such as benzophenone or 3,3'-dimethyl-4-methoxybenzophenone, 2-isopropylthioxanthone or 2,4-dimethylthioxanthone, 2 , thioxanthone compounds such as 4-diethylthioxanthone and 2,4-dichlorothioxanthone, amino benzene such as Michler's ketone and 4,4'-diethylaminobenzophenone Methyl ketone compound, 10-butyl-2-chloroacridone, 2-ethyl hydrazine, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, oxy-phenyl-acetic acid 2- A compound such as a mixture of [2-oxo-2-phenyl-ethoxycarbonyl-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester.

In addition, the photosensitizer which is an active energy ray-curable resin composition to be used in the present invention is not particularly limited, and examples thereof include an amine such as an aliphatic amine or an aromatic amine, and a urea such as o-tolylthiourea. A sulfur compound such as sodium ethyl dithiophosphate or s-benzyl isonamide-p-toluenesulfonate.

The photopolymerization initiator and the photosensitizer are preferably used in an amount of from 0.1 to 20% by mass, more preferably from 0.5 to 10% by mass, based on 100 parts by mass of the resin component in the active energy ray-curable resin composition.

Further, the active energy ray-curable resin composition used in the present invention may be blended with various additives as needed, or may be diluted with a solvent as needed. Examples of the additive include a polymerization inhibitor, an antioxidant, a leveling agent, an antifoaming agent, a coating surface improving agent (wetting property, a slidability improving agent, etc.), a plasticizer, a coloring agent, and inorganic fine particles.

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

In addition, in order to secure the adhesion of the hard coat layer to various film substrates and the like, an adhesiveness-imparting resin (hereinafter referred to as TF) can be suitably blended.

For the TF, a resin such as a phenol type such as a modified rosin, a polymerized rosin, a phenol resin or an alkylphenol resin, an aromatic petroleum system such as a coumarone oxime system, an aliphatic hydrocarbon system or a terpene resin can be used. A resin which has been modified with a carboxyl group and modified with a hydroxyl group can also be used.

Examples of the solvent to be used for the dilution include aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, and isopropanol, and esters such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate. Ketones such as ketoethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used singly or in combination of two or more.

[Method of Manufacturing Hard Coating Film]

The protective adhesive film of the present invention can be produced by applying the above-mentioned active energy ray-curable resin composition to a film substrate and hardening it to form a hard coat layer to form a hard coat film, and then having a film base material The opposite side of 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, spray coating, and suspension. Coating, dip 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 coating, 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 ultrahigh pressure mercury lamp, a metal halide lamp, an electrodeless lamp (melt lamp), a chemical lamp, a black lamp, and mercury. - Xenon lamps, short arc lamps, helium-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 20 μm, more preferably 5 to 15 μm. When the thickness is less than 5 μm, the surface pencil hardness is lowered; when it exceeds 25 μm, the adhesion coating is difficult due to the hardening shrinkage of the hard coat layer.

[hard coating film]

The hard coat film used in the present invention has at least the above-mentioned film base material and hard coat layer, and when the adhesive layer is laminated on a display portion of an image display device for use in a mobile phone, etc., from the viewpoint of actually exhibiting an anti-damage effect The pencil surface of the hard coat layer has a pencil hardness of at least 3H, 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 pencil 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, when the thickness of the adhesive layer is such a thickness, sufficient adhesion to the object to be adhered can be exhibited, and high stress can be maintained even when stress is concentrated on the surface of the protective adhesive film. The modulus of elasticity 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, an acrylic 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 preferably has a repeating unit containing an acrylate having a polar group such as a hydroxyl group, a carboxyl group or an amine group in the side chain or another vinyl monomer in a range of 0.01 to 15% by mass. The acrylic copolymer can be obtained by copolymerization by a solution polymerization method, a monolith 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 from 400,000 to 1,400,000, more preferably from 600,000 to 1,200,000.

Further, in order to increase the cohesive force of the adhesive, it is preferred to add a crosslinking agent. The crosslinking agent may, for example, be an isocyanate crosslinking agent, an epoxy crosslinking agent, or a chelate crosslinking agent. The amount of the crosslinking agent added is preferably adjusted so that the gel fraction of the adhesive layer becomes 25 to 80%. A better gel fraction is 40 to 75%. The most preferred is 50 to 70%. When the gel fraction is less than 25%, the surface pencil hardness will decrease when the protective adhesive film is adhered to the panel. On the other hand, when the gel fraction exceeds 80%, the adhesiveness is lowered. The cured adhesive layer was immersed in toluene, and the dried 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 adhesion-imparting resin may be added. The adhesiveness-imparting resin to be added to the adhesive layer of the adhesive tape of the present invention may be a rosin-based resin such as a rosin or a rosin esterified product, or a terpene-based resin such as a diterpene polymer or an α-pinene-phenol copolymer. A petroleum resin such as an aliphatic (C5) or an aromatic (C9), in addition to a styrene resin, a phenol resin, and a xylene resin. In order to set the b* value of the adhesive layer after standing at 100 ° C for 14 days to 6 or less, it is preferred to add a hydrogenated rosin having less unsaturated double bonds, an esterified product of uneven rosin, or an aliphatic or aromatic petroleum. Resin, etc.

In order to achieve both adhesion and yellowing resistance, it is preferred to use both a highly heterogeneous rosin ester and a polymerized rosin ester and a petroleum resin.

When the adhesive resin is an acrylic copolymer, the amount of the tackifier resin to be added is preferably 10 to 60 parts by mass based on 100 parts by mass of the acrylic copolymer. When attaching importance to adhesion, it is best to add 20 to 50 parts by mass. In addition, when the adhesive resin is a rubber-based resin, it is preferable to add 80 to 150 parts by mass of the tackifying resin to 100 parts by mass of the rubber-based resin. When the adhesive resin is an anthrone-based resin, an adhesive-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 improve adhesion to glass, a decane coupling agent in the range of 0.001 to 0.005 may be added. In addition to this, a plasticizer, a softener, a filler, a pigment, a flame retardant, or the like may be added.

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 onto the substrate film and dried, or may be applied to a separator (release sheet), dried, and then attached to the substrate film.

The adhesive used as the adhesive layer can suitably adjust the stress relaxation of the adhesive in a high temperature environment by setting the dynamic viscoelastic spectrum of the dynamic viscoelastic spectrum at a frequency of 1 Hz to be at least 1.0 × 10 ⁵ Pa at 80 ° C. Foaming of the adhesive layer at high temperatures. The upper limit of the storage elastic modulus is not particularly limited as long as it is a range in which the adhesive can be prepared, but from the viewpoint of practical adhesion and prevention of overflow during processing, it is preferably about 5.0 × 10 ⁵ Pa, and particularly preferably 3.0 ×. 10 ⁵ Pa or less.

Further, the dynamic viscoelastic spectrum of the adhesive used as the adhesive layer at a frequency of 1 Hz preferably has a storage elastic modulus at 20 ° C of 1.0 × 10 ⁵ Pa or more, more preferably 2.5 × 10 ⁵ Pa or more. By setting the storage elastic modulus to 1.0 × 10 ⁵ Pa or more, it is possible to suitably suppress the decrease in the surface hardness of the protective adhesive film caused by the adhesive.

[protective adhesive film]

The protective adhesive film of the present invention is a protective film having a total thickness of 60 to 150 μm, preferably 80 to 120 μm, in which the hard coat film is provided with an adhesive layer.

The protective film of the present invention has a configuration in which the physical properties of the constituent members are adjusted to a specific range, and it is possible to achieve the opposite characteristics such as deformation at the time of damage and stress concentration while achieving an extremely thin film of 150 μm or less. . Thereby, even if a special hard coat layer and a film base material having extremely high hardness and rigidity are not provided, 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 using a hard coat layer and a film base material having extremely high hardness and rigidity, it is difficult to cause peeling due to repulsion even when it is bonded to an adhering object.

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 can be preferably 2H or more, more preferably 3H or more in a state of being bonded to the glass. Hardness. A protective film for a thin glass panel as a portable electronic terminal and a protective film for various displays can be suitably used. In addition, when the adhering object is an object that causes cracking such as glass, it can be effectively used as a scattering preventing film that prevents scattering when the adhering object is broken.

The 180° peel adhesion force of the protective adhesive film of the present invention to the glass at a stretching speed of 300 mm/min is preferably 4 to 12 N/25 mm. By making the adhesion force into the above range, it is also difficult to cause the protective adhesive film to peel off from the end portion when used in a portable electronic terminal. Further, the light transmittance of the protective adhesive film of the present invention is preferably 85% or more, more preferably 90% or more. When the light transmittance is 85% or more, the visibility of the display portion of the image display device is improved.

[screen panel]

The screen panel of the present invention is composed of a laminate of a glass plate and the protective adhesive film of the present invention. Since the screen panel is less likely to be damaged on the surface layer, it can be effectively used for the image display portion 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 in a state of being bonded to a glass plate. In other words, since the screen panel is greatly reduced in damage to the glass panel, it 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, the chemical strengthening method includes an ion exchange method and an air-cooling strengthening method. Examples of the material of the glass plate include float glass, alkali glass, alkali-free glass, and tempered glass.

[Portable electronic terminal]

The portable electronic terminal device of the present invention is configured such that, in a casing having a liquid crystal display module (LCD Module), the laminated body of the protective film of the present invention, that is, the screen panel and the surface of the liquid crystal display module are fixed by a gap therebetween. (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 or the like is applied to the surface. When the bending occurs, stress is concentrated on the concave portion, and damage is likely to occur. However, even in such a case, the protective adhesive film of the present invention can appropriately prevent damage. Therefore, the protective adhesive film and the screen panel of the present invention can be particularly suitably used for the portable electronic terminal device of such a configuration.

In particular, as an example of a portable electronic terminal, there is a mobile phone whose screen panel is made of glass. Since the surface of the mobile phone carried by the person in the pocket, the bag, or the like of the trousers is easily damaged, the mobile phone screen panel of the protective adhesive film of the present invention having a surface hardness of 3H or more is not easily damaged, and can be reduced. Since the visibility of the image display portion is lowered, it is preferably used.

[Examples]

The invention will be more specifically described below by way of examples and comparative examples, but the invention is not limited to the examples.

(Synthesis Example 1)

<Synthesis of Polymer (A1)> In a flask having 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 1000 mass were added. Methyl isobutyl ketone (hereinafter referred to as MIBK) and 7.5 parts by mass of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) were heated to 90 ° C for 1 hour while stirring under a nitrogen stream. The reaction was carried out at 90 ° C for 1 hour. Next, a mixed liquid 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 added dropwise over 2 hours while stirring at 90 ° C, and then reacted at 100 ° C for 3 hours. Subsequently, 10 parts by mass of AIBN was added, and after reacting at 100 ° C for 1 hour, the temperature was raised to about 120 ° C, and the reaction was carried out for 2 hours. After cooling to 60 ° C, the nitrogen introduction tube was replaced with an air introduction tube, and 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 were added and mixed, and air was used. The reaction solution was heated to 110 ° C while foaming, and reacted for 8 hours. Subsequently, 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 to obtain a polymer (A1) (a 50% by mass MIBK solution of a nonvolatile component). Here, the obtained polymer (A1) had a weight average molecular weight of 11,000 (calculated from GPC in terms of polystyrene) and a (meth)acrylonitrile equivalent of 300 g/eq.

(Synthesis Example 2)

<Synthesis of Polymer (A2)> In a flask having 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), and 1.8 parts by mass of lauryl are added. The mercaptan, 1000 parts by mass of MIBK, and 7.5 parts by mass of AIBN were heated to 90 ° C over 1 hour while stirring under a nitrogen stream, and reacted at 90 ° C for 1 hour. Then, a mixed liquid composed of 600 parts by mass of GMA, 150 parts by mass of nBMA, 4.8 parts by mass of lauryl mercaptan, and 22.5 parts by mass of AIBN was added dropwise thereto at 90 ° C for 2 hours, followed by a reaction at 100 ° C for 3 hours. Subsequently, 10 parts by mass of AIBN was added, and after reacting at 100 ° C for 1 hour, the temperature was raised to about 120 ° C, and the reaction was carried out for 2 hours. After cooling to 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 was raised to 110 ° C and the reaction was carried out for 8 hours. Subsequently, 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 to obtain a polymer (A2) (a 50% by mass MIBK solution of a nonvolatile content). Here, the obtained polymer (A2) had a weight average molecular weight of 8,800 (available from GPC in terms of polystyrene) and a (meth)acrylonitrile equivalent of 240 g/eq.

(Synthesis Example 3)

<Synthesis of fluorinated alkyl acrylate (average addition functional group number 2)> In a 200 ml reaction flask, 48.2 g (0.1 mol) of perfluorooctylethyl thiol was added dropwise at room temperature with stirring at 28.9 g. (0.05 mol) a mixed solution of dipentaerythritol hexaacrylate (LUMICURE DPA-600 manufactured by Dainippon Ink and Chemicals Co., Ltd.), 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 50 ° C for 3 hours, and MIBK and triethylamine were distilled off under reduced pressure using an evaporator (bath temperature: 50 ° C or less) to obtain 76.8 g of a product (A3). The mixture contains the fluorinated alkyl acrylate represented by the above formula (xxi), and the addition reaction site of the acryl fluorenyl group and the perfluorooctyl ethyl thiol is different from the above structural formula (xxi). Compound. The desired synthesis was confirmed based on the peak and integral values of the ¹ H-NMR spectrum of the product.

¹ H-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 a MIBK solution (nonvolatile content: 50% by mass) of the polymer (A1) synthesized in Synthesis Example 1 and 50 parts by mass of pentaerythritol tetraacrylate (hereinafter referred to as PETA), 1 part by mass of hexaacrylate having dimethyloxane bond (Ebecryl 1360 manufactured by diacel.UCB Co., Ltd., hereinafter referred to as SiA) and 4 parts by mass of photopolymerization initiator (1) Hydroxycyclohexyl phenyl ketone (hereinafter referred to as HCPK) was diluted with ethyl acetate to a nonvolatile content of 40% by mass to obtain a hard coating agent (1).

(Preparation of Hard Coating Agent (2)) 100 parts by mass of MIBK solution (nonvolatile content: 50% by mass) of the polymer (A2) synthesized in Synthesis Example 2, 50 parts by mass of PETA, 1 part by mass of SiA and 4 were uniformly mixed. The mass fraction of HCPK was 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)) 100 parts by mass of a MIBK solution (nonvolatile content: 50% by mass) of the polymer (A1) synthesized in Synthesis Example 1 and 50 parts by mass of pentaerythritol tetraacrylate (hereinafter referred to as PETA), 1 part by mass of the above-prepared A3 (synthesis example 3) 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 (3).

(Production of Hard Coating Film (1)) The above-prepared hard coating agent (1) 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, and dried at 60 ° C. After 90 seconds, ultraviolet light was irradiated by an ultraviolet irradiation device (F450, lamp: 120 W/cm, H valve) in an air atmosphere to irradiate ultraviolet rays with an irradiation amount of 0.5 J/cm ^{2 to} form a thickness. 8 μm hard coat. Next, the non-hard-coated surface was subjected to surface treatment by a corona treatment apparatus so that the surface tension was 55 dyne/cm, thereby obtaining a hard coat film (1).

(Production of Hard Coating Film (2)) A hard coating film (1) used in place of the hard coating film (1) described above was used in the same manner as in the hard coating agent (2) prepared above, and a hard coating film was obtained in the same manner. (2).

(Production of Hard Coating Film (3)) The above-prepared hard coating agent (1) 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, and dried at 60 ° C. After 90 seconds, ultraviolet light was irradiated by an ultraviolet irradiation device (F450, lamp: 120 W/cm, H valve) in an air atmosphere to irradiate ultraviolet rays with an irradiation amount of 0.5 J/cm ^{2 to} form a thickness. 15 μm hard coat. Next, the non-hard-coated surface was subjected to surface treatment by a corona treatment device so that the surface tension was 55 dyne/cm, thereby obtaining a hard coat film (3).

(Production of Hard Coating Film (4)) A hard coating agent (1) was applied to one surface of a polyethylene terephthalate film having a modulus of elasticity of 4.5 GPa and a thickness of 50 μm, and dried at 60 ° C for 90 seconds. After that, an ultraviolet ray irradiation apparatus (F450, lamp: 120 W/cm, H valve manufactured by Japan Co., Ltd.) was used in an air atmosphere to irradiate ultraviolet rays with an irradiation 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 subjected to surface treatment by a corona treatment device so that the surface tension was 55 dyne/cm, thereby obtaining a hard coat film (4).

(Production of Hard Coating Film (5)) A hard coating agent (1) 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, and dried at 60 ° C for 90 seconds. After that, an ultraviolet ray irradiation apparatus (F450, lamp: 120 W/cm, H valve manufactured by Japan Co., Ltd.) was used in an air atmosphere to irradiate ultraviolet rays with an irradiation amount of 0.5 J/cm ^{2 to} form a hard coat layer having a thickness of 3 μm. . Next, the non-hard-coated surface was subjected to surface treatment by a corona treatment device so that the surface tension was 55 dyne/cm, thereby obtaining a hard coat film (5).

(Production of Hard Coating Film (6)) On one surface of a polyethylene terephthalate film having a modulus of elasticity of 4.5 GPa and a thickness of 50 μm, a hard coat layer having a thickness of 2 μm was applied by a corona treatment device. The non-hard-coated surface of the hard coating film (surface pencil hardness: 3H) was subjected to surface treatment so that the surface tension was 55 dyne/cm, thereby obtaining a hard coating film (6).

(Production of Hard Coating Film (7)) The above-prepared hard coating agent (3) was applied to one surface of a polyethylene terephthalate film having a modulus of elasticity of 4.5 GPa and a thickness of 100 μm, and dried at 60 ° C. After 90 seconds, an ultraviolet irradiation device (F450, lamp: 120 W/cm, H valve manufactured by Japan Co., Ltd.) was used in an air atmosphere to irradiate ultraviolet rays with an irradiation amount of 0.5 J/cm ^{2 to} form a thickness of 15 μm. Hard coating. Next, the non-hard-coated surface was subjected to surface treatment by a corona treatment device so that the surface tension was 55 dyne/cm, thereby obtaining a hard coat film (7).

(Measurement of the surface pencil hardness of the hard coat film) The hardness obtained above was measured by the pencil scratch tester (manual type) of the coating film manufactured by the company Jingyuan Co., Ltd. according to the regulations of JIS K5600-5-4 (1999 edition). The surface pencil hardness of the coating film (1) to (7). Here, the measured surface pencil hardness is shown in Table 1.

(Preparation of Adhesive Layer (1)) An adhesive solution was applied to a release liner obtained by forming an anthrone compound release layer on one surface of a polyethylene terephthalate film having a thickness of 75 μm (relative to 100). The mass of the adhesive made by Japan Ink Chemical Co., Ltd. SPS1030B is compounded with 1.3 parts by mass of isocyanate-based crosslinking agent (Ronett L-45 manufactured by Japan Polyurethane Co., Ltd., solid content 45%), and dried at 90 ° C for 90 seconds to form The adhesive layer (1) having a thickness of 10 μm after drying.

(Preparation of Adhesive Layer (2)) An adhesive solution was applied to a release liner obtained by forming an anthrone compound release layer on one surface of a polyethylene terephthalate film having a thickness of 75 μm (relative to 100). The mass of Japan's Ink Chemical Co., Ltd. made the adhesive SPS1030B with 1.3 parts by mass of isocyanate cross-linking agent (Ronett L-45 manufactured by Japan Polyurethane Co., Ltd., solid content 45%), and dried at 90 ° C for 90 seconds to form The adhesive layer (2) having a thickness of 30 μm after drying.

(Preparation of Adhesive Layer (3)) An adhesive solution was applied to a release liner obtained by forming an anthrone compound release layer on one surface of a polyethylene terephthalate film having a thickness of 75 μm (relative to 100). The mass portion of Toyo Ink Co., Ltd. made adhesive BPS5762K with 1.6 parts by mass of hardener BXX5627), and dried at 90 ° C for 90 seconds to form a dried adhesive layer (3) having a thickness of 10 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 film having a thickness of 93 μm. . The obtained protective adhesive film was adhered to the glass plate, and the microhardness was measured under the conditions of a press-in depth of 1 μm and a press-in time of 15 seconds using the ultra-hardness tester Fischer apparatus H100C X-Yprog manufactured by Fischer Instruments. It is 270N/mm ² .

(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 adhesive film having a thickness of 93 μm. .

(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 kg/cm, it was aged at 40 ° C for 2 days to obtain a protective adhesive film having a thickness of 100 μm. .

(Example 4) After the adhesive layer (1) was bonded to the corona-treated surface of the hard coat film (4) under a pressure of 4 kg/cm, it was aged at 40 ° C for 2 days to obtain a protective adhesive film having a thickness of 75 μm. .

(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, it was aged at 40 ° C for 2 days to obtain a protective adhesive film having a thickness of 125 μm. . 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 310 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, it was aged at 40 ° C for 2 days to obtain a protective adhesive film having a thickness of 88 μm. .

(Comparative Example 2) After the adhesive layer (2) was bonded to the corona-treated surface of the 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 film having a thickness of 113 μm. .

(Comparative Example 3) After the adhesive layer (1) was bonded 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 to obtain a protective adhesive film having a thickness of 62 μm. .

(Comparative Example 4) After the adhesive layer (3) was bonded to the corona-treated surface of the hard coat film (1) under a pressure of 4 kg/cm, the film was aged at 40 ° C for 2 days to obtain a protective adhesive film having a thickness of 113 μm. .

[Determination of pencil hardness on the surface of protective adhesive film]

The protective adhesive film obtained in the above examples and comparative examples was adhered to a glass plate, and a pencil scratch tester for a coating film manufactured by the company Jingyuan Co., Ltd. was used according to the regulations of JIS K5600-5-4 (1999 edition). Manually) The surface pencil hardness was measured.

[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 a parallel disc having a diameter of 7.9 mm was mounted on the Aes 2KSTD of the viscoelasticity testing machine manufactured by Ray-Europe. The test piece was sandwiched in a parallel disk, and the viscoelastic spectrum was measured by a temperature dispersion method, a frequency of 1 Hz, a measurement temperature range of -30 ° C to 100 ° C, and a storage elastic modulus G' of 20 ° C and 80 ° C was read.

[observe the presence or absence of bubbles]

The lining glass of the sarcophagus glass with a diagonal of 2 inches and a thickness of 0.8 mm which was chemically strengthened at normal temperature and normal pressure was bonded to the same size and the adhesive sheet of the comparative example as a test piece. .

The test piece was subjected to a pressure cooker treatment at 50 ° C and 5 kgf/m ² for 20 minutes, and the number of bubbles at the time of pasting was measured by a 50-fold microscope at the center and the four corners of the test piece at five points. Subsequently, it was placed in an environmental tester at 60 ° C, 90% RH. After standing, a 50-fold microscope was used to observe whether there were bubbles at 5 points in the center and four corners of the sample. The determination was made as follows: ○: no bubbles, ×: bubbles were present.

[adhesion]

The adhesive force of the adhesive tape of the present invention is determined by the following procedure in accordance with JIS-Z0237 (2000) Test Method for 180-degree Peel Adhesion.

Under the conditions of an ambient temperature of 23 ° C and a humidity of 50%, the adhesive tape of the example and the comparative example, which was lined with a 25 μm polyester film, was pressed back and forth on the glass plate by a 2 kg roller at a time of 1 hour, and left for 1 hour. The Tensilon universal tensile tester (manufactured by Orientec, RTA100) was used to perform stretching at a temperature of 300 mm/min under the same temperature and humidity conditions, and peeling was performed at 180 degrees, and the adhesion force (N) at the time of peeling off the adhesive tape of 25 mm width was measured.

As is apparent from the above Table 1, the protective adhesive film of the present invention can maintain a high surface hardness and a suitable adhesive force even if the total thickness is thin, and it is difficult to generate bubbles even in a high temperature environment.

(industrial use)

The protective adhesive film of the present invention, for example, for the protective use of a thin glass panel for a portable electronic terminal, can be suitably used because of its high surface pencil hardness. Or it can be suitably used for the protective use 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 which prevents scattering when the adhering object is broken, and has a great industrial significance.

1. . . Protective adhesive film

2. . . glass plate

3. . . framework

4. . . LCD module

5. . . Void

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a portable electronic terminal of the present invention.

1. . . Protective adhesive film

2. . . glass plate

3. . . framework

4. . . LCD module

5. . . Void

Claims (10)

A protective adhesive film which is provided with a hard coat film formed of a film substrate having a hard coat layer and provided with an adhesive layer; wherein the film base material has an elastic modulus of 3 to 7 GPa and a thickness of 38 Å. 100 μm; 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 3H or more; the thickness of the adhesive layer is 5 to 20 μm; the total thickness is 60 to 150 μm; The adhesive layer has a storage elastic modulus of 80×10 at a frequency of 1 Hz in a dynamic viscoelastic spectrum of 1.0×10 ⁵ Pa or more; the hard coat layer is composed of a polymer (A) having a (meth)acryl fluorenyl group and a layer composed of a cured product of an active energy ray-curable resin composition of a polyfunctional (meth) acrylate (B) having three or more (meth) acrylonitrile groups in one molecule, The polymer (A) of the propylene fluorenyl group has a (meth) acrylate-based polymer (a1) having a reactive functional group in the side chain, and α, β-non having a functional group reactive with the reactive functional group. The saturated compound (a2) is obtained by a reaction. The protective adhesive film of claim 1, wherein the adhesive layer has a storage elastic modulus of at least 1.0 × 10 ⁵ Pa at 20 ° C in a dynamic viscoelastic spectrum at a frequency of 1 Hz. For example, in the protective adhesive film of claim 1, the 180 peel adhesion force of the glass plate at a tensile speed of 300 mm/min is 4 to 12 N/25 mm. For example, the protective adhesive film of claim 1 of the patent scope, wherein the polymerization The material (A) is a reaction product obtained by reacting a glycidyl (meth)acrylate polymer with an α,β-unsaturated carboxylic acid. The protective adhesive film of claim 1, wherein the polymer (A) has a weight average molecular weight of 5,000 to 80,000, and the (meth) acrylonitrile equivalent is 100 to 300 g/eq. The protective adhesive film of claim 1, wherein the active energy ray-curable resin composition contains a fluorinated alkyl (meth) acrylate, and the fluorinated alkyl (meth) acrylate A functional group having a fluorinated alkyl group at the terminal represented by the following general formula (1) and two or more (meth) acrylonitrile groups, wherein the general formula (1) is: In the formula (1), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is an alkylene chain which may have a hetero atom or a linking group represented by the following formula (2), and Rf is a fluorine atom. The alkyl group, the formula (2) is: In the formula (2), Y is an oxygen atom or a sulfur atom, and m and n may be the same or different, and may be an integer of 1 to 4, and Rf ¹ is a fluorinated alkyl group]. The protective adhesive film of claim 6, wherein the fluorine-containing alkyl (meth) acrylate contains a fluorine atom in one molecule. The ratio is 25% by weight or more and the molecular weight is 500 to 4,000. For example, the protective adhesive film of the first application of the patent scope, wherein the light transmittance is 85% or more. A screen panel comprising a protective adhesive film according to any one of claims 1 to 8 and a laminated body of a glass plate having a thickness of 0.1 to 1 mm. A portable electronic terminal device is characterized in that, in a casing having an LCD module, the screen panel of claim 9 is fixed to be spaced apart from the surface of the LCD module.