TW201601907A - Protective adhesive film, image display device, and portable electronic terminal - Google Patents

Abstract

The problem to be solved by the present invention is to provide a protective adhesive film that can prevent damage to a polarized plate or the like caused by touch entry or the like even if disposed on the surface of the polarized plate without an interposed glass substrate. The present invention relates to a protective adhesive film comprising an adhesive layer with a thickness of at least 15 [mu]m on at least one surface of a hard-coated film and having a total thickness of at least 150 [mu]m, wherein the hard-coated film comprises a hard-coating layer on at least one surface of a resin film with a thickness of at least 130 [mu]m, and the hard-coating layer has on the surface thereof a Martens hardness of at least 250 N/mm2, such hardness being measured by pressing a Vickers indenter that has face angles of 136 DEG into the surface of the hard-coating layer with a load of 1 mN.

Description

Protective adhesive film, image display device and portable electronic terminal

The present invention relates to a protective adhesive film for protecting the surface of an information display device such as a liquid crystal display or an organic electroluminescence display.

Portable electronic terminals such as portable computers, electronic notebooks, and mobile phones are required to be further lightweight and thinner. Accordingly, the information display device provided in the portable electronic terminal device is also required to be lighter and thinner.

The above information display device is known as a so-called on-cell or in-cell liquid crystal module equipped with a touch panel function.

However, the liquid crystal module described above has a problem that a pressure which may be generated when a touch is input causes a depression or damage of the polarizing plate constituting the liquid crystal module.

For example, a method of preventing a damage of a polarizing plate due to pressure is provided, for example, a method in which a glass substrate is placed closer to a surface side than the polarizing plate, and a hard coating film is provided on a surface of the glass substrate (for example, Patent Document 1).

However, the above-mentioned glass substrate is relatively expensive, and the portable electronic terminal device obtained by using the above-mentioned glass substrate tends to be heavy, and thus it is impossible to cope with the reduction in thickness and weight required by the industry.

For example, the surface of the optical film such as a polarizing plate constituting the information display device may be attached to a conventional hard coating without being interposed between the glass substrate or the like. Membrane.

However, since the conventional hard coating film is generally thin and soft, it is easily deformed by the pressure generated when the information display device is touch-inputted, and as a result, the polarizing plate is easily damaged.

Further, when the hard coat film is attached to the surface of an optical film such as a polarizing plate, an adhesive layer may be provided between the two.

However, if the adhesive layer is a film, generally, it may cause damage such as depression of the optical film; and if the adhesive layer is a thick film, generally, the surface of the hard coating film is easy. The problem of injury.

When the hard coating film is attached to an optical film such as a polarizing plate without a rigid body such as a glass substrate, the damage of the optical film is not caused, and the hard coating film body can be prevented. Damaged films are in demand in the industry.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-095064

[Problems to be solved by the invention]

The problem to be solved by the present invention is to prevent damage to an optical film caused by touch input or the like even when a rigid body such as a glass substrate is attached to a surface of an optical film such as a polarizing plate, and the body is It is also not easy to damage the protective adhesive film. [Means for solving the problem]

The inventors of the present invention have proposed a protective adhesive film to solve the aforementioned problems; the protective adhesive film has a total thickness of 150 μm of the adhesive layer (B) having a thickness of 15 μm or more on the side of at least one side of the hard coat film (A). The above protective adhesive film is characterized in that the hard coat film (A) has a hard coat layer (a2) on the side of at least one side of the resin film (a1) having a thickness of 130 μm or more, and the inter-angle angle 136 is The Vickers indenter was pressed into the surface of the hard coat layer (a2) at a load of 1 mN and measured to have a Martens' hardness of 250 N/mm ² or more. [Effects of the Invention]

The protective adhesive film of the present invention can prevent surface damage of the protective adhesive film even when subjected to partial pressure due to impact or touch input, and can prevent damage of an optical film such as a polarizing plate or Deformation (depression, etc.).

The protective adhesive film of the present invention is a protective adhesive film having a total thickness of the adhesive layer (B) having a thickness of 15 μm or more and a total thickness of 150 μm or more on the side of at least one side of the hard coat film (A), which is characterized in that: The coating film (A) has a hard coat layer (a2) on the side of at least one side of the resin film (a1) having a thickness of 130 μm or more, and the Vickers pressure at an angle of 136° is pressed into the load at a load of 1 mN. The surface of the hard coat layer (a2) was measured and found to have a Martens hardness of 250 N/mm ² or more.

The protective adhesive film of the present invention prevents the surface of the protective adhesive film from being damaged, and prevents damage or deformation of the optical film even when directly attached to the surface of the adherend such as an optical film. In view of the above, it is preferable to use a total thickness of 150 μm or more. The protective adhesive film is desirably used as an adhesive film specifically for protecting the surface of the information display device, and is more preferably used as a polarizing plate for protecting surfaces of so-called in-line and stacked information display devices. The optical film is used as an adhesive film.

For the protective adhesive film, a thickness of 150 μm to 500 μm is preferably used, and a thickness of 150 μm to 400 μm is preferably used, and a thickness of 150 μm to 350 μm is used, since the optical film can be prevented even when directly attached to the surface of the optical film. It is more desirable because it is damaged and contributes to the reduction in thickness and weight of the final product such as a portable electronic terminal.

The hard coat film (A) constituting the protective adhesive film is used for having a hard coat layer (a2) on at least one side of the resin film (a1) having a thickness of 130 μm or more.

The hard coat film (A) is preferably used in the case where the hard coat layer (a2) is provided directly on one side of the resin film (a1) or in another layer, and is used for the resin film (a1). When the hard coat layer (a2) is provided directly on the surface, it is preferable to reduce the thickness and weight of the portable electronic terminal.

Further, the hard coating film (A) was obtained by pressing a Vickers pressure of 136 ° between the edges of the hard coat layer (a2) at a load of 1 mN and measuring to have a Martens hardness of 250 N/ Mm ² or more. Here, the protective adhesive film produced by using the hard coat film having a Martens hardness of less than 250 N/mm ^{2 has} a surface hardness which is remarkably low, so that the above problem cannot be solved.

Should the Martens hardness of 250N / mm ² ~ 800N / mm ² of the range, preferably in the range of ^{250N / mm 2 ~ 500N / mm} 2 of, 250N / mm ² ~ 450N / mm ² of the range, since the hard coating can be prevented It is preferable that the film (A) is damaged and the crack is easily suppressed during the cutting process when it is directly attached to an optical film or the like.

Here, the Martens hardness refers to preparing a hard coating film (A) provided with a hard coat layer (a2) on one or both sides of the resin film (a1), and placing it on the surface of a smooth glass plate. The hard coat layer (a2) was placed on the upper surface, and the surface (the surface composed of the hard coat layer (a2)) was pressed and measured at a load of 1 mN to a Vickers pressure of 136°.

Further, in the hard coating film (A), it is preferable that the pencil hardness of the surface formed by the hard coat layer (a2) constituting the hard coating film (A) is 3H or more, and the surface pencil hardness is 4H or more. When the adhesive layer (B) is laminated on the hard coat film (A) to form a protective adhesive film, the surface hardness can be suppressed from being lowered, and as a result, it can be made higher. At the same time, it is preferable to prevent the damage of the hard coat film (A) from being prevented from being deformed or damaged by the optical film or the like.

The resin film (a1) constituting the hard coating film (A) is a thickness of 130 μm or more. Thereby, it is possible to obtain a protective adhesive film which can effectively prevent damage of the optical film even when directly attached to an optical film or the like.

The thickness is preferably in the range of 130 μm to 300 μm, and the thickness is in the range of 150 μm to 250 μm, so that it is preferable to obtain a protective adhesive film which can effectively prevent damage of the optical film even when directly attached to an optical film or the like. .

As the resin film (a1), a resin film capable of designing the hard coat film (A) to have a Martens hardness of 250 N/mm ² or more can be suitably selected.

For the resin film (a1), for example, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene naphthalate film, a polyethylene film, or a polypropylene film can be used. , cellophane film, diethyl phthalocyanine film, triethylene fluorene cellulose film, acetonitrile cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene -vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polyfluorene film, polyether ether ketone film, polyether ruthenium film, polyether phthalimide film, poly phthalate An amine film, a fluororesin film, a nylon film, an acrylic resin film, or the like.

When the elastic modulus of the range of 3 GPa to 15 GPa is selected as the resin film (a1), a hard coating film (A) having a Martens hardness of 250 N/mm ² or more is preferable, and since the protective adhesive is used, When the film is bonded, the resin film is not easily deformed, and the reduction in the surface hardness of the protective adhesive film can be effectively suppressed, which is preferable. Further, by using the resin film (a1) having the elastic modulus in the above range, the protective adhesive film finally obtained can be made relatively soft, and as a result, the protective adhesive film can be easily followed when attached to, for example, a gentle curved surface portion. The curved surface portion is preferred.

When the transparent film is used as the resin film (a1), it is preferable because the protective adhesive film is provided on the surface of the display of the information display device to ensure good visibility. The total light transmittance of the resin film (a1) is preferably 85% or more, preferably 88% or more, and particularly preferably 90% or more.

The resin film (a1) can be used for the purpose of further improving the adhesion to the hard coat layer (a2).

Further, the resin film (a1) may be subjected to a sandblasting method or a solvent treatment method for the purpose of further improving the adhesion to the hard coat layer (a2) or the adhesive layer (B). Surface treatment such as surface roughening treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet irradiation treatment, oxidation treatment, etc.

As the resin film (a1), a resin film containing an antistatic agent or the like can be used.

The antistatic agent may, for example, be a polyoxyethylene alkyl ether, a polyoxyethylene alkylphenol, a polyoxyethylene alkylamine or a polyoxyethylene alkyl group which is a nonionic antistatic agent. Indoleamine, fatty acid polyethylene glycol ester, sorbitan fatty acid ester (Sorbitan Fatty Acid Ester), polyoxyethylene sorbitan fatty acid ester, fatty acid glyceride, alkyl polyethyleneimine, and the like. The cationic antistatic agent may, for example, be an alkylamine salt, an alkyl fourth ammonium salt or an alkyl imidazoline derivative. Further, an acrylate compound having ethylene oxide in the skeleton or the like can also be used.

Further, as the antistatic agent, polyaniline, polypyrrole, polythiophene, poly 3,4-ethylenedioxythiophene which is a conductive polymer, and derivatives thereof can be used. The antistatic agent may also be a metal oxide-doped ytterbium-doped tin oxide (ATO), a tin-doped indium oxide (ITO), an aluminum-doped zinc oxide, a bismuth oxide or the like. Further, as the antistatic agent, an ion conductive antistatic agent in which a metal ion such as lithium ion is mixed may be used.

The hard coat layer (a2) constituting the hard coat film (A) was pressed into the surface of the hard coat layer (a2) at a load of 1 mN using a Vickers pressure of 136 ° at an interangle angle as described above and measured. The Martens hardness can be 250N/mm ² or more.

The hard coat layer (a2) may, for example, be a cured layer formed using various hard coating agents, and may be, for example, a layer formed using a hard coating agent containing an active energy ray-curable composition.

The hard coat layer (a2) is preferably used in a thickness of 3 μm to 25 μm, preferably 4 μm to 20 μm in thickness, and a thickness of 5 μm to 16 μm can be used to prevent damage to the hard coat film (A). A viewpoint of a protective film which can effectively prevent damage of an optical film when attached to an optical film or the like, and a hard coat which is prevented from being hardened and contracted by a hard coating agent at the time of forming the hard coat layer (a2) The viewpoint of the film (A) and the warpage of the protective adhesive film is better.

A hard coating agent which can be used for the formation of the hard coat layer (a2) is obtained from the viewpoint of obtaining a hard coat film (A) having a Martens hardness in the above range, and a hard coat layer containing (meth) acrylate is preferably used. In the viewpoint of suppressing the hardening shrinkage of the hard coating agent and forming a hard coat layer having high surface hardness and durability, a hard coating agent containing a polyurethane (meth) acrylate (X) is more preferable.

As the polyurethane (meth) acrylate (X), various urethane (meth) acrylates can be used, and among them, a urethane (meth) acrylate having four or more (meth) acrylonitrile groups in the molecule is used. The viewpoint of obtaining a hard coat film (A) having a Martens hardness of 250 N/mm ² or more is preferable.

The polyaminoester (meth) acrylate having four or more (meth) acrylonitrile groups in the above molecule is preferably used, for example, by reacting a polyisocyanate with a hydroxyl group-containing (meth) acrylate.

As the polyisocyanate, for example, an aliphatic polyisocyanate such as hexamethylene diisocyanate, a diisocyanate diisocyanate or an isocyanuric acid triisocyanate; norbornane diisocyanate, isophorone diisocyanate or methylene double ( 4-cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5 An alicyclic polyisocyanate such as diisocyanylcyclohexane.

As the polyisocyanate, a trimer of the above aliphatic polyisocyanate or alicyclic polyisocyanate may also be used.

When hexamethylene diisocyanate which is an aliphatic diisocyanate, norbornane diisocyanate of a cycloaliphatic diisocyanate, and isophorone diisocyanate are used as said polyisocyanate, the Martens hardness is 250 N/mm<^2> or more. The viewpoint of the hard coat film (A) is preferable, since the damage of the hard coat film (A) can be prevented, and the damage of the optical film can be more effectively prevented even when it is directly attached to an optical film or the like. Preferably.

The above-mentioned hydroxyl group-containing (meth) acrylate which can be used for the production of the aforementioned polyurethane (meth) acrylate (X), for example, trimethylolpropane di(meth) acrylate, ethylene oxide modified three Hydroxymethylpropane di(meth)acrylate, propylene oxide modified trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, bis((meth)acryloyloxyethyl Hydroxyethyl isocyanurate, neopentyl alcohol tri(meth) acrylate, ditrimethylolpropane tri(meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. It is used alone or in combination of two or more of these.

When neopentyl alcohol tri(meth)acrylate or dipentaerythritol penta (meth) acrylate is used as the hydroxy group-containing (meth) acrylate, durability such as scratch resistance is further improved. A hard coat film of the hard coat layer (a2) is preferred.

The polyurethane (meth) acrylate (X) may be subjected to a urethanization reaction of the polyisocyanate with the hydroxy group-containing (meth) acrylate in the presence of a urethane catalyst in a conventional manner. Manufacturing.

As the urethane catalyst, for example, an amine compound such as pyridine, pyrrole, triethylamine, diethylamine or dibutylamine; a phosphide such as triphenylphosphine or triethylphosphine; and dilauric acid can be used. An organic zinc compound such as butyltin, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate or tin octylate, or an organic zinc compound such as zinc octoate.

The polyurethane (meth) acrylate (X) obtained by the above method may be used singly or in combination of two or more.

A polyurethane ester acrylate obtained by using norbornane diisocyanate as the polyisocyanate and a polyurethane ester acrylate obtained by using isophorone diisocyanate as the polyisocyanate are used as the aforementioned polyurethane (meth)acrylate (X). The viewpoint of obtaining a hard coating film (A) having a Martens hardness of 250 N/mm ² or more is preferable, since the damage of the hard coating film (A) can be prevented, and the film is directly attached to the optical film or the like. It is also preferable to prevent the damage of the optical film more effectively.

Further, a polyurethane (meth) acrylate obtained by using an isocyanurate such as bis((meth)acryloyloxyethyl)hydroxyethyl isocyanurate, and the aforementioned polyurethane (meth) acrylate are used. It is preferable to use a combination of the above-mentioned polyurethane (meth)acrylate (X) to obtain a hard coating film (A) having a Martens hardness of 250 N/mm ² or more, since a hard coating film can be prevented ( A) is preferable because it is more effective in preventing damage of the optical film even when it is directly attached to an optical film or the like.

By using the polyurethane (meth) acrylate as a combination as described above, the Martens hardness having the above range can be obtained, and the warpage of the hard coating film due to the hardening shrinkage can be effectively suppressed, and the surface hardness is high. Hard coating film with excellent durability.

As the hard coating agent which can be used for the formation of the hard coat layer (a2), those containing other (meth) acrylates other than the aforementioned polyurethane (meth) acrylate (X) can be used.

The other (meth) acrylate may, for example, be a polyfunctional (meth) acrylate (Y) having three or more (meth) acrylonitrile groups in the molecule.

The above polyfunctional (meth) acrylate (Y), for example, trimethylolpropane tri(meth) acrylate, ethylene oxide modified trimethylolpropane tri(meth) acrylate, epoxy Propane modified trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ginseng (2-(A) Base propylene oxyethyl)isocyanurate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol tri(meth) acrylate , dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc., used alone or in combination Two or more types are used.

The polyfunctional (meth) acrylate (Y) further enhances the durability of the hard coat layer (a2) such as scratch resistance, and it is preferred to use a (meth) acrylonitrile equivalent of 50 g/eq. The range of ~200 g/eq. is preferably in the range of 70 g/eq. to 150 g/eq., and more preferably, the (meth) acrylonitrile equivalent is 80 g/ Range of eq.~120g/eq. A polyfunctional (meth) acrylate having a (meth) acryl oxime equivalent of the above range may, for example, be neopentyl alcohol tetraacrylate (propylene decyl equivalent: 88 g/eq.) or dipentaerythritol (Meth) acrylate (acrylonitrile equivalent: 118 g/eq.) or the like.

The above polyfunctional (meth) acrylate (Y) is preferably used in combination with the aforementioned polyurethane (meth) acrylate (X).

The mass ratio [(X)/(Y)] of the polyaminoester (meth) acrylate (X) to the polyfunctional (meth) acrylate (Y) described above forms a hard coat having a Martens hardness of the aforementioned range. The film (A) and the viewpoint of further improving the durability such as scratch resistance of the hard coat layer (a2) are preferably in the range of 90/10 to 10/90, preferably in the range of 80/20 to 20/80. More preferably in the range of 75/25 to 25/75.

The total amount of the polyaminoester (meth) acrylate (X) and the polyfunctional (meth) acrylate (Y) to be used is preferably 10 parts by mass based on 100 parts by mass of the nonvolatile component of the hard coating agent. 99.95 parts by mass, preferably 20 parts by mass to 99.5 parts by mass.

A hard coating agent which can be used for the formation of the aforementioned hard coat layer (a2), in addition to the foregoing, a single (A) group having one (meth)acryloyl group in the molecule can be used without departing from the effects of the present invention. Other (meth) acrylates such as acrylates and di(meth)acrylates having two (meth) acrylonitrile groups in the molecule. The amount of use is preferably 40 parts by mass or less, preferably 20 parts by mass, based on 100 parts by mass of the total of the polyurethane (meth) acrylate (X) and the polyfunctional (meth) acrylate (Y). the following.

As the hard coating agent which can be used for the formation of the aforementioned hard coat layer (a2), a photopolymerization initiator containing a photopolymerization initiator capable of initiating a hardening reaction by irradiation with an active energy ray can be used.

The photopolymerization initiator can be exemplified by an intramolecular cracking type photopolymerization initiator and a dehydrogenation type photopolymerization initiator. The intramolecular splitting type photopolymerization initiator may, for example, be diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, or oligo[2-hydroxy-2-methyl 1-[4-(1-methylvinyl)phenyl]acetone], benzyldimethylacetal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane 1-ketone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- Oxo (4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Acetophenone-based compound such as phenylphenyl)-butanone; benzoin such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 2,4,6-trimethylphenylene diphenyl A fluorenylphosphine-based compound such as phosphine oxide or bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide; benzil, methylphenylglyoxylate Wait.

On the other hand, examples of the dehydrogenation type photopolymerization initiator include benzophenone, o-benzhydrylbenzoic acid methyl-4-phenylbenzophenone, and 4,4'-dichlorobenzophenone. Hydroxybenzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide, propylene deuterated benzophenone, 3,3',4,4'-tetrakis (tertiary butylperoxycarbonyl) a benzophenone compound such as benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone or 4-methylbenzophenone; a thioxanthone compound such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone or 2,4-dichlorothioxanthone; (Michler's Ketone), an aminobenzophenone compound such as 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylhydrazine, 9,10- Phenanthrene, camphorquinone, 1-[4-(4-benzylidylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propane-1- Ketones, etc. These photopolymerization initiators may be used singly or in combination of two or more.

Further, as the hard coating agent, those containing a photosensitizer can be used.

As the photosensitizer, for example, a tertiary amine compound such as diethanolamine, N-methyldiethanolamine or tributylamine, a urea compound such as o-tolylthiourea, sodium diethyldithiophosphate or s-benzyl can be used. A sulfur compound such as isothiourea-p-toluenesulfonate or the like.

The amount of the photopolymerization initiator and the photosensitizer to be used is preferably 0.05 parts by mass to 20 parts by mass, preferably 0.5 parts by mass to 10 parts by mass per 100 parts by mass of the non-volatile component of the hard coating agent. Share. Further, when ionizing radiation such as an electron beam, an α line, a β line, or a γ line is used as the active energy ray, it is not necessary to use a photopolymerization initiator or a photosensitizer.

As the hard coating agent, those containing a solvent can be used.

The solvent may, for example, be acetone, isobutanol, 2-propanol, isoamyl alcohol, diethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether, ethylene glycol single Methyl ether, o-dichlorobenzene, xylene, cresol, chlorobenzene, isobutyl acetate, isopropyl acetate, isoamyl acetate, ethyl acetate, n-butyl acetate, n-propyl acetate, n-amyl acetate , methyl acetate, cyclohexanol, cyclohexanone, 1,4-two Alkane, dichloromethane, N,N-dimethylformamide, styrene, tetrachloroethylene, tetrahydrofuran, 1,1,1-trichloroethane, toluene, n-hexane, 1-butanol, 2-butyl Alcohol, methanol, methyl isobutyl ketone, methyl ethyl ketone, methyl cyclohexanol, methyl cyclohexanone, methyl n-butyl ketone, or the like may be used alone or in combination of two or more of them.

The hard coating agent may be an antifouling agent containing an active energy ray-curable compound (Z) having a fluorine atom and a ruthenium atom for the purpose of imparting antifouling properties, anti-fingerprint adhesion, and the like.

As the active energy ray-curable compound (Z) having a fluorine atom and a ruthenium atom, for example, a compound having a fluorocarbon chain, a siloxane chain, or a hydrocarbon chain can be used. In particular, any one or both of a fluorocarbon chain and a siloxane chain can be used as the active energy ray-curable compound (Z).

In the above-mentioned active energy ray-curable compound (Z), it is preferred to use a poly(perfluoroalkylene ether) chain as a fluorocarbon chain and a cyclopoxane structure, and it is preferred to use a cyclopentasiloxane structure. a structure in which a divalent linking group is bonded to both ends of a poly(perfluoroalkylene ether) chain, and a (meth)acrylonyl group is bonded to the above-mentioned cyclopolyoxyalkylene via a divalent linking group. Compound (z1).

The poly(perfluoroalkylene ether) chain of the compound (z1) is exemplified by a structure in which a divalent fluorinated carbon group having 1 to 3 carbon atoms and an oxygen atom are bonded to each other. The divalent fluorinated carbon group having 1 to 3 carbon atoms may be one type or a combination of two or more types. Specifically, the following formula (1) can be exemplified.

【化1】

(In the above formula (1), X is the following formula (1-1) to (1-5), and X may be any one of the following formulae (1-1) to (1-5), or may be Two or more of the following formulae (1-1) to (1-5) exist in a random form or in a block form. Further, n is an integer of 2 to 200 representing a repeating unit.

[Chemical 2]

The poly(perfluoroalkylene ether) chain is further composed of the perfluoromethylene group represented by the above formula (1-1) and the perfluoroethyl group represented by the above formula (1-2). The poly(perfluoroalkylene ether) chain is preferred in terms of improving stain resistance and smoothness.

The molar ratio of the perfluoromethylene group represented by the above formula (1-1) to the perfluoroethyl group represented by the above formula (1-2) [perfluoromethylene group represented by the above formula (1-1) / the foregoing The perfluoroextension ethyl group represented by the formula (1-2) is preferably in the range of from 1/10 to 10/1. Further, the value of n in the above formula (1) is preferably in the range of 2 to 200, preferably in the range of 10 to 100, more preferably in the range of 20 to 80.

The cyclopoxane structure contained in the above compound (z1) is, for example, a structure represented by the following formula (2).

[化3]

(In the above formula (2), R ¹ is a methyl group, R ³ is a divalent organic group bonded to a poly(perfluoroalkylene ether) chain, and R ⁴ is a group having a (meth)acryl fluorenyl group. The price is organic. In addition, m is an integer from 2 to 5.)

The cyclopentaoxane structure is preferably a cyclotetrahydroxane structure in which m in the above formula (2) is 3.

The divalent linking group of the above-mentioned bonded poly(perfluoroalkylene ether) chain and the cyclic polyoxyalkylene structure is not particularly limited as long as it is a divalent organic group, and for example, the following formula (3) can be exemplified. .

【化4】

(In the above formula (3), Y is an alkylene group having 1 to 6 carbon atoms.)

In addition, the divalent linking group of the (meth) acrylonitrile group and the (meth) acryl fluorenyl group are not particularly limited as long as they are a divalent organic group, and examples thereof include the following formula (4).

【化5】

(In the above formula (4), Z ¹ , Z ² and Z ³ are each independently an alkylene group having 1 to 6 carbon atoms.)

The aforementioned compound (z1) can be produced, for example, by the following steps (1) to (3). (1) reacting a compound having an allyl group at both ends of a poly(perfluoroalkylene ether) chain with a cyclopolyoxyalkylene compound having a hydrofluorenyl group in the presence of a platinum-based catalyst to obtain a poly( A step of a compound having a cyclic polyoxyalkylene structure at both ends of the perfluoroalkylene ether chain. (2) a step of reacting the compound obtained in (1) with an allyloxyalkanol in the presence of a platinum-based catalyst, and adding a hydroxyl group to the cyclic polyoxyalkylene structural moiety of the compound obtained in (1). (3) A step of reacting an isocyanate group-containing (meth) acrylate with a (2) addition hydroxy group to introduce a (meth) acrylonitrile group.

The content of the active energy ray-curable compound (Z) such as the compound (z1) obtained by the above method is preferably in the range of 0.05 part by mass to 5 parts by mass based on 100 parts by mass of the non-volatile component of the hard coating agent. The content of the range of parts by mass to 2 parts by mass is more preferable in view of achieving superior surface hardness and stain resistance.

Further, the hard coating agent may optionally contain a polymerization inhibitor, a surface conditioner, an antistatic agent, an antifoaming agent, a viscosity adjusting agent, a light stabilizer, a weathering stabilizer, a heat stabilizer, an ultraviolet absorber, and an antistatic agent. Additives such as oxidizing agents, coating agents, organic pigments, inorganic pigments, pigment dispersants, cerium oxide beads, organic beads; inorganic fillers such as cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, and antimony pentoxide.

The hard coat film (A) used in the present invention can be produced, for example, by applying and hardening the hard coating agent on one surface or both surfaces of the resin film (a1) to form a hard coat layer (a2).

The method of applying the aforementioned hard coating agent to the above-mentioned resin film (a1) can be, for example, gravure coating, roll coating, comma coating, air knife coating, conformal coating, and spray coating. , pass-over coating, dip coating, spin coating, wheeler coating, brush coating, solid coating by a silk screen, wire bar coating Printing methods such as coating, flow coating, etc., lithography, and typography.

The method of applying the above-mentioned hard coating agent to the above-mentioned resin film (a1), and further using the gravure coating, roll coating, corner wheel coating, air knife coating, conformal coating, and wire bar coating described above The method of cloth, flow coating, etc. is preferred because it can form a hard coat layer (a2) having a more uniform thickness.

A method of curing the hard coating agent, for example, the hard coating agent contains the polyurethane (meth) acrylate (X), a polyfunctional (meth) acrylate (Y), and an active energy ray-curable compound ( The active energy ray-curable composition such as Z) may be a method in which an active energy ray is applied to a coated surface obtained by applying the hard coating agent and dried to be cured.

Examples of the active energy ray include ionizing radiation of ultraviolet rays, electron beams, α lines, β lines, and γ lines.

The apparatus for irradiating the active energy ray, for example, in the case of ultraviolet rays, may be exemplified by a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), a chemical lamp, a black lamp, and mercury. - Xenon lights, short arc lamps, cadmium cadmium lasers, argon lasers, sunlight, LEDs, etc.

When the ultraviolet ray is irradiated to form the hard coat layer (a2), the ultraviolet ray irradiation suppresses the oxygen barrier of the radical polymerization, and it is preferably carried out in a passive gas atmosphere such as nitrogen.

Further, when the hard coat layer (a2) is formed, heating or the like may be performed after the irradiation of the active energy ray as necessary, or the active energy ray may be irradiated after heating.

Next, the adhesive layer (B) constituting the protective adhesive film of the present invention will be described.

The adhesive layer (B) has an ideal adhesive force for the adherend such as a polarizing plate, and can prevent damage of the hard coat film (A), and can be directly attached to an optical film or the like. From the viewpoint of effectively preventing such damage, it is preferable to use a thickness of 15 μm or more.

Preferably, the adhesive layer (B) has a thickness in the range of 15 μm to 150 μm, preferably a thickness in the range of 20 μm to 140 μm, and more preferably a thickness in the range of 20 μm to 130 μm. More preferably, a thickness having a thickness in the range of 20 μm to 110 μm is used, and a thickness having a thickness in the range of 20 μm to 60 μm is more preferably used, and a thickness of a range of 20 μm to 45 μm is used to obtain an adherend for an optical film or the like. The viewpoint of a protective adhesive film having an ideal adhesive force and a high surface hardness is more preferable.

The above-described problem to be solved by the present invention is not limited to the case where the thickness of the adhesive layer (B) is set to 15 μm or more, but by the hard coating film having a specific Martens hardness. (A), the total thickness of the protective adhesive film and other technical matters can be combined with each other.

The adhesive layer (B) has a dynamic viscoelastic spectrum phase at a frequency of 1 Hz, and the storage elastic modulus at 20 ° C is preferably 1.0 × 10 ⁵ Pa to 5.0 × 10 ⁵ Pa, preferably 1.5 × 10 ⁵ Pa to 4.5 × The storage elastic modulus of 10 ⁵ Pa, 2.0×10 ⁵ Pa~4.0×10 ⁵ Pa, because it can maintain the high surface hardness of the protective adhesive film, even on the surface of the protective adhesive film due to, for example, touch input or impact. In the case where local pressure is generated, damage to the adherend such as an optical film can be alleviated, and deformation and depression of the polarizing plate or the like can be effectively prevented, which is preferable.

The adhesive layer (B) can be formed by applying an adhesive or the like. An acrylic adhesive, a rubber-based adhesive, an anthrone-based adhesive, or the like can be used as the adhesive.

In particular, the use of an acrylic adhesive containing an acrylic polymer as the adhesive further improves the adhesion to the hard coating film (A), transparency, weather resistance, and the like. good.

As the acrylic polymer, a polymerizable (meth)acrylic monomer can be used. As the (meth)acrylic acid monomer, for example, a (meth) acrylate can be exemplified, and a (meth) acrylate containing an alkyl group having 2 to 14 carbon atoms is preferably used.

The (meth) acrylate having an alkyl group having 2 to 14 carbon atoms may, for example, be ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-butyl acrylate or acrylic acid. Butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, isodecyl acrylate, lauryl acrylate, methyl methacrylate Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, butyl methacrylate, butyl methacrylate, n-hexyl methacrylate, Cyclohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, isodecyl methacrylate, lauryl methacrylate Wait.

The (meth) acrylate is preferably an alkyl (meth) acrylate having an alkyl group having 4 to 9 carbon atoms as described above, and more preferably an alkyl group having 4 to 9 carbon atoms. Alkyl acrylate.

N-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, ethyl acrylate in the alkyl acrylate having an alkyl group having 4 to 9 carbon atoms, which is easy to ensure ideal adhesion The relay is better.

The amount of the (meth) acrylate having an alkyl group having 2 to 14 carbon atoms is preferably in the range of 90 parts by mass to 99 parts by mass based on 100 parts by mass of the total amount of the (meth)acrylic acid monomer. When the amount is in the range of 90 parts by mass to 96 parts by mass, it is preferable because it is easy to ensure an ideal bonding force.

As the acrylic polymer, for example, a polar group having a hydroxyl group, a carboxyl group or a guanamine group can be used.

The acrylic polymer can be produced, for example, by polymerizing a (meth)acrylic monomer containing a (meth)acrylic monomer having a polar group such as a hydroxyl group, a carboxyl group or a guanamine group.

Examples of the hydroxyl group-containing (meth) acrylate monomer include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. Hydroxypropyl (meth)acrylate, caprolactone modified (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and the like. Among these, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate are preferred.

The above-mentioned carboxyl group-containing (meth) acrylate monomer may, for example, be acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, acrylic acid or methacrylic acid 2-polymer, ethylene oxide modification. Succinic acid acrylate and the like. Among these, acrylic acid is preferred.

The above-mentioned (meth) acrylate monomer having a mercapto group, for example, may be exemplified by N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and acrylonitrile. Porphyrin, acrylamide, N,N-dimethylpropenamide, 2-(perhydrophthalic acid imine-N-yl)ethyl acrylate, and the like. Among these, N-vinyl-2-pyrrolidone, N-vinyl caprolactam, and acrylonitrile are used. Porphyrin is preferred.

Examples of the other polar group-containing vinyl monomer include vinyl acetate, acrylonitrile, maleic anhydride, and itaconic anhydride.

The amount of the (meth)acrylic monomer having a polar group is preferably in the range of 0.1% by mass to 20% by mass based on the total amount of the (meth)acrylic monomer used for the production of the acrylic polymer. In the range of 1% by mass to 13% by mass, when the amount is in the range of 1.5% by mass to 8% by mass, it is more preferable to adjust the cohesive force, the holding power, and the adhesiveness to an appropriate range.

The weight average molecular weight of the acrylic polymer is preferably from 400,000 to 1,400,000, preferably from 600,000 to 1,200,000. By setting the weight average molecular weight, it is easy to adjust the adhesive force to a specific range, and when the protective adhesive film is formed, it is easy to appropriately alleviate the partial pressure generated during impact or touch input.

Further, the aforementioned weight average molecular weight can be measured by gel permeation chromatography (GPC). More specifically, "SC8020" manufactured by Tosoh Corporation can be used as a GPC measuring device, and it can be obtained by measuring the following GPC measurement conditions using a polystyrene-converted value. (Measurement conditions for GPC) ・Sample concentration: 0.5% by mass (tetrahydrofuran solution) ・Sample injection amount: 100 μL ・Dissolved solution: Tetrahydrofuran (THF) ・Flow rate: 1.0 mL/min ・Column temperature (measured temperature): 40 °C ・Pipe column: "TSKgel GMHHR-H" manufactured by Tosoh Co., Ltd. ・Detector: Differential refractometer

In view of further improving the cohesive force of the above-mentioned binder, it is preferable to use a crosslinking agent in addition to the above-mentioned acrylic polymer.

Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, and a chelate crosslinking agent.

The crosslinking agent is preferably used in a range in which the gel fraction of the formed adhesive layer is in the range of 25% by mass to 85% by mass, preferably in the range of 40% by mass to 80% by mass. When it is used in a range of 50% by mass to 75% by mass of the gel fraction, it is possible to suppress the decrease in the hardness of the surface pencil when the protective adhesive film of the present invention is attached to a member such as a polarizing plate. Fully adhesive. Further, in the gel fraction of the present invention, the cured adhesive layer is immersed in toluene, and after standing for 24 hours, the dried mass of the remaining insoluble matter is measured, and is expressed as a percentage with respect to the original mass.

The above-mentioned adhesive further improves the adhesive strength, and those containing a tackifying resin can be used.

The amount of the adhesion-imparting resin to be added is preferably in the range of 10 parts by mass to 60 parts by mass based on 100 parts by mass of the acrylic polymer. When the adhesion is more important, the amount thereof is preferably in the range of 20 parts by mass to 50 parts by mass.

As the above-mentioned binder, those known in the art may be used in addition to the above-mentioned additives.

In the case of the above-mentioned additive, for example, in order to improve the adhesion to the glass substrate or the metal member, it is preferable to add a decane coupling agent in a range of 0.001 part by mass to 0.005 part by mass based on 100 parts by mass of the binder. Further, a plasticizer, a softener, a filler, a pigment, a flame retardant or the like as another additive may be added as needed.

The protective adhesive film of the present invention can be directly coated and dried by using the one or both sides of the hard coat film (A) obtained by the above method, preferably on one side. The adhesive layer (B) is formed to be manufactured.

Further, in the protective adhesive film of the present invention, the adhesive layer (B) obtained by applying and drying the above-mentioned adhesive on the surface of the release liner can be transferred to the above-mentioned method. On the one hand or both sides of the hard coating film (A), it is preferably one side to be manufactured.

When the hard coating film (A) has a hard coat layer on both sides, the adhesive layer (B) is preferably provided on the surface side of the hard coat layer on one side thereof. Further, when the hard coating film (A) has a hard coat layer (a2) on only one side, the adhesive layer (B) is preferably provided on the resin film on the side where the hard coat layer (a2) is not provided. The surface side of (a1).

When the protective adhesive film of the present invention is formed by adjusting the physical property value and the thickness of the hard coat film (A) and the adhesive layer (B) in a specific range and combined, it is input due to impact or touch. When the local pressure is applied to the protective adhesive film, the stress can be appropriately alleviated, so that the damage to the adhered member can be suppressed, and the height of the surface of the protective adhesive film can be reduced, so that the height can be achieved. Damage prevention.

The protective adhesive film of the present invention has a high surface hardness. Specifically, the pencil protective film of the protective adhesive protective film in a state in which the protective adhesive film is attached to the glass plate is preferably 2H or more, and more preferably 3H or more. Therefore, the protective adhesive film of the present invention can be preferably used as a protective adhesive film for an image display portion of a portable electronic terminal device or a protective adhesive film for various displays.

The laminate of the present invention is a laminate of the protective adhesive film and the polarizing plate of the present invention.

Conventionally, in the manufacture of an information display device, a protective adhesive film and a polarizing plate are mainly laminated on a glass substrate.

However, since the glass substrate is a rigid body, there is a problem that the laminate cannot be wound into a tubular shape or the like.

Further, since the glass substrate is thick and heavy, there is a possibility that the information display device can be made thinner and lighter.

Since the laminate of the present invention is obtained by attaching the protective adhesive film to a polarizing plate directly or with a soft resin film without using a conventional thick glass substrate, it can be wound into a cylindrical shape or the like. The above-mentioned laminate is produced by a so-called roll to roll, and the production efficiency can be improved more than ever.

The polarizing plate used in the present invention can generally be used for laminating a polarizer protective layer on both sides of a polarizing plate.

The polarizer can be produced by using a polyvinyl alcohol resin. The polyvinyl alcohol-based resin can be produced by saponifying a polyvinyl acetate-based resin.

The polarizer sheet can be produced, for example, by adsorbing a dichroic dye to a film-formed polyvinyl alcohol-based resin film.

Further, the polarizing plate can be produced by laminating a polarizer protective layer such as a triethylene fluorene cellulose film on both sides of the polarizing plate obtained as described above via an adhesive layer.

As the aforementioned dichroic dye, iodine or a dichroic organic dye can be used. The polyvinyl alcohol-based resin film is dyed with a dichroic dye, and the polyvinyl alcohol-based resin film can be obtained by immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dyes. When iodine is used as the dichroic dye, a method in which a polyvinyl alcohol-based resin film is immersed in an aqueous solution containing iodine and potassium iodide and dyed is usually used.

The polarizer protective layer is not particularly limited. However, when it is used as a display material, it is preferable to use a resin which is excellent in transparency.

The polarizer protective layer may, for example, be polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane.玢, 醯 醯 cellulose film, triethylene fluorene cellulose film, acetonitrile cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film , polystyrene film, polycarbonate film, cycloolefin resin film, polymethylpentene film, polyfluorene film, polyether ether ketone film, polyether ruthenium film, polyether phthalimide film, polyimine A film, a fluororesin film, a nylon film, an acrylic resin film, or the like.

Further, when the polarizer protective layer is formed on both surfaces of the polarizer layer, a polarizer protective layer made of a different resin can be formed on each surface. For example, a polarizer protective layer made of a triacetyl cellulose film may be formed on one surface of the polarizer layer, and a polarizer protective layer made of a cycloolefin resin film may be formed on the other surface.

The use of the polarizing plate having a thickness of 50 μm to 200 μm is preferable because it can contribute to weight reduction and thinning of the information display device and the portable electronic terminal.

[Information display device and portable electronic terminal device] The information display device of the present invention can be, for example, a device in which a liquid crystal display module (LCD module) and a protective adhesive film of the present invention are laminated, preferably in a composition. The surface of the polarizing plate of the liquid crystal display module directly laminates the device for protecting the adhesive film.

For the liquid crystal display module described above, it is desirable to use, for example, an in-line or stacked liquid crystal display module having a touch panel function. In the above-mentioned embedded or stacked liquid crystal display module having a touch panel function, the outermost surface of the information display portion is often a polarizing plate. Therefore, in the information display device of the present invention, it is preferable that the protective adhesive film is directly attached to the surface of the polarizing plate constituting the liquid crystal display module.

The information display device in which the protective adhesive film is directly attached to a polarizing plate can be preferably used for, for example, a portable electronic terminal, a large display, a vehicle display, or the like. In particular, it is preferably used in a portable electronic terminal or a vehicle-mounted display that often has a touch panel function.

The information display device of the present invention can be manufactured, for example, by laminating a liquid crystal display module manufactured in advance with the protective adhesive film.

Moreover, the information display device of the present invention can be manufactured by laminating the above-mentioned laminated body comprising the protective adhesive film and the polarizing plate, and a liquid crystal display panel (LCD), for example, with an adhesive tape having high transparency. Since the laminate has flexibility to be bendable, when it is bonded to a liquid crystal display panel which is generally rigid, bubbles are less likely to be trapped at the interfaces, and as a result, the production efficiency of the information display device can be particularly improved.

Since the above-described configuration has a configuration composed of the above-described laminate, the surface layer is less likely to be damaged, and the depression of the polarizing plate due to local stress is less likely to occur. Therefore, the above-described configuration should be employed as a portable electronic terminal that can easily withstand local stress caused by dropping or the like. [Examples]

Hereinafter, the present invention will be more specifically described by way of examples and comparative examples.

(Synthesis Example 1: Synthesis of Polyurethane Acrylate (A1)) In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 250 parts by mass of butyl acetate and 206 parts by mass of norbornane diisocyanate were added. 0.5 parts by mass of oxyphenol and 0.5 parts by mass of dibutyltin diacetate, and the temperature was raised to 70 ° C while blowing air, and pentaerythritol triacrylate (hereinafter referred to as "PE3A") was added dropwise for 1 hour. A mixture of alcohol tetraacrylate (hereinafter referred to as "PE4A") (mixture of a mass ratio of 75/25) of 795 parts by mass.

After completion of the dropwise addition, the reaction was continued at 70 ° C for 3 hours, and further, the reaction was further carried out until the infrared absorption spectrum of 2250 cm ^-1 showing the isocyanate group disappeared to obtain a butyl acetate solution containing the polyurethane acrylate (A1) and PE4A. (80% by mass of the nonvolatile component, hereinafter referred to as "polyurethane acrylate (A1) solution"). The molecular weight (calculated value) of the aforementioned polyurethane acrylate (A1) was 802.

(Synthesis Example 2: Synthesis of Polyurethane Acrylate (A2)) 254 parts by mass of butyl acetate and 222 parts by mass of isophorone diisocyanate were added to a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer. 0.5 parts by mass of methoxyphenol and 0.5 parts by mass of dibutyltin diacetate were added, and after heating to 70 ° C, 795 parts by mass of a mixture of PE3A and PE4A (mixture of a mass ratio of 75/25) was added dropwise over 1 hour.

After the completion of the dropwise addition, the reaction was continued at 70 ° C for 3 hours, and further, the reaction was further carried out until the infrared absorption spectrum of 2250 cm ^-1 showing the isocyanate group disappeared to obtain a butyl acetate solution containing the polyurethane acrylate (A2) and PE4A. (80% by mass of the nonvolatile component, hereinafter referred to as "polyurethane acrylate (A2) solution"). The molecular weight (calculated value) of the aforementioned polyurethane acrylate (A2) was 818.

(Synthesis Example 3: Synthesis of Polyurethane Acrylate (A3)) In a flask equipped with a stirrer, a gas introduction tube, a cooling tube, and a thermometer, 254 parts by mass of butyl acetate and 222 parts by mass of isophorone diisocyanate were added. 0.5 parts by mass of methoxyphenol and 0.5 parts by mass of dibutyltin diacetate, and after heating to 70 ° C, 369 parts by mass of bis(acryloyloxyethyl)hydroxyethyl isocyanurate was added dropwise over 1 hour, and PE3A and A mixture of PE4A (mixture of a mass ratio of 75/25) of 398 parts by mass.

After the completion of the dropwise addition, the reaction was continued at 70 ° C for 3 hours, and further, the reaction was further carried out until the infrared absorption spectrum of 2250 cm ^-1 showing the isocyanate group disappeared to obtain a butyl acetate solution containing the polyurethane acrylate (A3) and PE4A. (80% by mass of the nonvolatile component, hereinafter referred to as "polyurethane acrylate (A3) solution"). The molecular weight (calculated value) of the aforementioned polyurethane acrylate (A3) was 889.

(Preparation Example 1: Preparation of Hard Coating Agent (HC1)) 31.3 parts by mass of the polyurethane acrylate (A1) solution obtained in Synthesis Example 1 and 31.3 parts by mass of the polyurethane acrylate (A2) solution obtained in Synthesis Example 2, 25 parts by mass of the polyurethane acrylate (A3) solution obtained in Synthesis Example 3, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (dipentaerythritol hexaacrylate / dioxon tetra Alcohol pentaacrylate = 60/40 (mass ratio) 30 parts by mass, reactive fluorine antifouling agent (OPTOOL DAC-HP; manufactured by Daikin Industries Co., Ltd., non-volatile content 20% by mass) 2.0 parts by mass and light 4.5 parts by mass of a polymerization initiator ("IRGACURE 184" manufactured by BASF JAPAN Co., Ltd., 1-hydroxycyclohexyl phenyl ketone) was uniformly stirred, and then diluted with ethyl acetate to prepare a hard coat of 40% by mass of a nonvolatile matter. Cloth (HC1).

(Preparation Example 2: Preparation of Hard Coating Agent (HC2)) 31.3 parts by mass of the polyurethane acrylate (A1) solution obtained in Synthesis Example 1 and 31.3 parts by mass of the polyurethane acrylate (A2) solution obtained in Synthesis Example 2, 25 parts by mass of the polyurethane acrylate (A3) solution obtained in Synthesis Example 3, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (dipentaerythritol hexaacrylate / dioxon tetra Alcohol pentaacrylate = 60/40 (mass ratio) 105 parts by mass, reactive fluorine antifouling agent (OPTOOL DAC-HP; manufactured by Daikin Industries Co., Ltd., non-volatile content 20% by mass) 2.0 parts by mass and light 4.5 parts by mass of a polymerization initiator ("IRGACURE 184" manufactured by BASF JAPAN Co., Ltd., 1-hydroxycyclohexyl phenyl ketone) was uniformly stirred, and then diluted with ethyl acetate to prepare a hard coat of 40% by mass of a nonvolatile matter. Cloth (HC2).

(Production Example 1) 100 parts by mass of SK DYNE 909A (acrylic adhesive), and CORONATE L-45 (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate-based crosslinking agent, solid) The component was 45 mass%) 0.7 parts by mass and stirred for 15 minutes, thereby preparing an adhesive.

Next, the adhesive is applied to a release liner having a thickness of 25 μm after drying to form a release layer of an anthrone compound on one side of a polyethylene terephthalate film having a thickness of 75 μm, and The adhesive layer (1) was formed by drying at 75 ° C for 5 minutes.

(Production Example 2) The adhesive layer (2) was obtained in the same manner as in Production Example 1 except that the thickness of the adhesive layer was changed from 25 μm to 50 μm.

(Production Example 3) The adhesive layer (3) was obtained in the same manner as in Production Example 1 except that the thickness of the adhesive layer was changed from 25 μm to 100 μm.

(Production Example 4) The adhesive layer (4) was obtained in the same manner as in Production Example 1 except that the thickness of the adhesive layer was changed from 25 μm to 10 μm.

(Production Example 5) 24 parts by mass of n-butyl acrylate, 75 parts by mass of 2-methoxyethyl acrylate, and acrylic acid 2 were mixed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen inlet. 1 part by mass of hydroxyethyl ester, 0.2 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator, and 100 parts by mass of ethyl acetate, and after nitrogen substitution in the reaction vessel, at 80 ° C This was allowed to polymerize for 8 hours, whereby an acrylic copolymer having a weight average molecular weight of 700,000 was obtained.

Next, the acrylic copolymer and ethyl acetate were mixed, whereby an adhesive having a solid content of the acrylic copolymer of 30% by mass was obtained.

Next, 100 parts by mass of the above-mentioned binder and 0.1 parts by mass of CORONATE HX (isocyanate-based crosslinking agent, solid content: 75 mass%) of CORONATE HX (available from Nippon Polyurethane Co., Ltd.) were mixed and stirred for 15 minutes to be dried. After the thickness was 50 μm, the release liner was applied to a release layer of an anthrone compound on one side of a polyethylene terephthalate film having a thickness of 75 μm, and dried at 75 ° C for 5 minutes. This forms an adhesive layer (5).

(Example 1) The hard coating agent (1) was applied on one side of a polyethylene terephthalate film (COSMOSHINE A4300 manufactured by Toyobo Co., Ltd.) having a thickness of 188 μm using a bar coater. After drying at 80 ° C for 90 seconds, an ultraviolet irradiation device ("F450" manufactured by Fusion UV Systems Japan Co., Ltd., bulb: 120 W/cm, H bulb) was used in an air atmosphere, and ultraviolet rays were irradiated with an amount of light of 0.5 J/cm ² . Thereby, a hard coat film having a hard coat layer having a thickness of 12 μm was obtained.

Next, the adhesive layer (1) was bonded to the surface of the hard coating film formed of the polyethylene terephthalate film at a pressure of 4 kg/cm, and aged at 40 ° C for 2 days. Thereby, a protective adhesive film (1) having a thickness of 225 μm was obtained.

(Example 2) A polyethylene having a thickness of 280 μm was replaced with a polyethylene terephthalate film having a thickness of 250 μm, and a thickness of 287 μm was obtained in the same manner as in Example 1. Protect the adhesive film (2).

(Example 3) A protective adhesive film (3) having a thickness of 250 μm was obtained in the same manner as in Example 1 except that the above-mentioned adhesive layer (2) was used instead of the above-mentioned adhesive layer (1).

(Example 4) A protective adhesive film (4) having a thickness of 300 μm was obtained in the same manner as in Example 1 except that the above-mentioned adhesive layer (3) was used instead of the above-mentioned adhesive layer (1).

(Example 5) A polyethylene terephthalate film having a thickness of 280 μm was replaced by a polyethylene terephthalate film having a thickness of 250 μm, and the above-mentioned adhesive layer was replaced with the above-mentioned adhesive layer (2). (1) A protective adhesive film (5) having a thickness of 312 μm was obtained in the same manner as in Example 1 except for the above.

(Example 6) A polyethylene terephthalate film having a thickness of 280 μm was replaced by a polyethylene terephthalate film having a thickness of 250 μm, and the above-mentioned adhesive layer was replaced with the above-mentioned adhesive layer (3). (1) A protective adhesive film (6) having a thickness of 362 μm was obtained in the same manner as in Example 1 except for the above.

(Example 7) A protective adhesive film (7) having a thickness of 225 μm was obtained in the same manner as in Example 1 except that the hard coating agent (2) was used instead of the hard coating agent (1).

(Example 8) The thickness was obtained in the same manner as in Example 1 except that the hard coating agent (2) was used instead of the hard coating agent (1), and the thickness of the hard coat layer was changed from 12 μm to 6 μm. 219μm protective adhesive film (8).

(Example 9) A protective adhesive film (9) having a thickness of 225 μm was obtained in the same manner as in Example 1 except that the adhesive layer (5) was used instead of the above-mentioned adhesive layer (1).

(Example 10) A protective adhesive film (10) having a thickness of 228 μm was obtained in the same manner as in Example 1 except that the thickness of the hard coat layer was changed from 12 μm to 15 μm.

(Example 11) A protective adhesive film (11) having a thickness of 219 μm was obtained in the same manner as in Example 1 except that the thickness of the hard coat layer was changed from 12 μm to 6 μm.

(Example 12) A protective adhesive film (12) having a thickness of 217 μm was obtained in the same manner as in Example 1 except that the thickness of the hard coat layer was changed from 12 μm to 4 μm.

(Comparative Example 1) The hard coating agent (1) was applied on one side of a polyethylene terephthalate film (COSMOSHINE A4300 manufactured by Toyobo Co., Ltd.) having a thickness of 125 μm using a bar coater. After drying at 80 ° C for 90 seconds, an ultraviolet irradiation device ("F450" manufactured by Fusion UV Systems Japan Co., Ltd., bulb: 120 W/cm, H bulb) was used in an air atmosphere, and ultraviolet rays were irradiated with an amount of light of 0.5 J/cm ² . Thereby, a hard coat film having a hard coat layer having a thickness of 12 μm was obtained.

Next, the adhesive layer (1) was bonded to the surface of the hard coating film formed of the polyethylene terephthalate film at a pressure of 4 kg/cm, and aged at 40 ° C for 2 days. Thereby, a protective adhesive film (13) having a thickness of 162 μm was obtained.

(Comparative Example 2) A thickness of 137 μm was obtained in the same manner as in Example 1 except that a polyethylene terephthalate film having a thickness of 100 μm was used instead of the polyethylene terephthalate film having a thickness of 188 μm. Protect the adhesive film (14).

(Comparative Example 3) A film having a thickness of 112 μm was obtained in the same manner as in Example 1 except that a polyethylene terephthalate film having a thickness of 75 μm was used instead of the polyethylene terephthalate film having a thickness of 188 μm. Protect the adhesive film (15).

(Comparative Example 4) A protective adhesive film (16) having a thickness of 213 μm was obtained in the same manner as in Example 1 except that the hard coat layer was not formed.

(Comparative Example 5) A thickness of 214 μm was obtained in the same manner as in Example 1 except that the thickness of the hard coat layer was changed from 12 μm to 1 μm, and the adhesive layer (1) was used instead of the adhesive layer (1). Protective adhesive film (17).

(Comparative Example 6) A thickness of 210 μm was obtained in the same manner as in Example 1 except that the above-mentioned adhesive layer (4) was used instead of the above-mentioned adhesive layer (1), and the thickness thereof was changed from 25 μm to 10 μm. Protect the adhesive film (18).

The following evaluations were made for the protective adhesive films obtained in the above examples and comparative examples. The results obtained are shown in Tables 1 to 3.

(Measurement Method of Storage Elasticity Coefficient) The storage elastic modulus of the above-mentioned adhesive layer was measured using a viscoelasticity tester (manufactured by Rheometrics Co., Ltd., trade name: Ares 2kSTD). Specifically, a test piece was sandwiched between parallel disks of the measuring unit of the test machine, and the storage elastic modulus (G') at 20 ° C was measured at a frequency of 1 Hz. The test piece used for the above measurement was obtained by cutting the adhesive layer obtained in the above-mentioned production example into a circular shape having a thickness of 1 mm and a diameter of 8 mm.

(Martens hardness of hard coating film) The hard coating film of the unbonded adhesive layer is placed on the glass plate with the hard coating layer thereon, and fixed by the Saifufen tape. angle. Thereafter, Ficker SCOPE HM2000Xyp (FISCHER INSTRUMENTS Co., Ltd.) was used to press the Vickers pressure of 136° at an angle of 1 mN for 20 seconds and measure the Martens hardness of the surface of the hard coat layer.

By measuring the pencil hardness and the stress relaxation property of the surface of the protective adhesive film, it is evaluated whether or not the damage of the polarizing plate or the like due to the touch input or the like can be prevented.

(Measurement of pencil hardness of protective adhesive film) The protective adhesive film obtained in the above examples and comparative examples was attached to a glass plate, and the hardness H~ was used in accordance with JIS K 5600-5-4 (1999 edition). A pencil of 4H and a pencil-scraping type tester (manual type) of a coating film manufactured by Imoto Seisakusho Co., Ltd. were used to measure the pencil hardness of the surface (hard coat layer).

(Evaluation of stress relaxation property 1) A polyethylene terephthalate film having a thickness of 6 μm having a black matte side as a substitute for a polarizing plate is attached to the surface of the adhesive layer constituting the protective adhesive film. And the one obtained by the above attachment is used as a test piece. The attachment is performed such that the black matte surface constituting the polyethylene terephthalate film is on the front side (the side not contacting the surface of the adhesive layer).

Next, the test piece was placed on the glass plate so that the hard coat layer of the protective adhesive film constituting the test piece was on the upper side, and the four corners were fixed by the celluloid adhesive tape.

Next, using a pencil scraping type tester (manual type) of a coating film manufactured by Imoto Seisakusho Co., Ltd., in accordance with the method specified in JIS K 5600-5-4 (1999 edition), a pencil scraping with a hardness of 4H was used. The surface of the previously fixed test piece composed of a hard coat layer is rubbed.

The black matte surface on the back side of the position scraped by the aforementioned pencil was visually observed to see whether or not the scratch was visible. The evaluation is based on the following criteria.

◎ scratch marks were not observed at all.

○ Confirm that there is a pale white line due to scratch marks.

△ It was confirmed clearly that there was a white line due to scratches.

× A line having a convex shape due to scratches was clearly confirmed.

(Evaluation of Stress Relief 2) The load was changed from 750 g to 1 kg, and the evaluation was carried out in the same manner and on the basis of the method described in the section "Evaluation of Stress Relief 1".

The evaluation results are shown in Tables 1 to 3 below. Further, the PET in the table means polyethylene terephthalate.

【table 3】

As is apparent from the above Tables 1 to 3, the protective adhesive film of the present invention has an ideal surface hardness and can achieve excellent stress relaxation. On the other hand, in the protective adhesive films of Comparative Examples 1 to 3, although the same hard coater and adhesive as in Example 1 were used, the surface hardness or stress relaxation was caused because the composition of the present invention was not sufficiently satisfied. Poor. Further, the protective adhesive film of Comparative Example 4 had a low surface hardness because it had no hard coat layer. The protective adhesive film of Comparative Example 5 was inferior in surface hardness and stress relaxation. The protective adhesive film of Comparative Example 6 caused a decrease in stress relaxation when the load was increased.

Claims (7)

The protective adhesive film is a protective adhesive film having a total thickness of the adhesive layer (B) having a thickness of 15 μm or more and a total thickness of 150 μm or more on the side of at least one side of the hard coat film (A), which is characterized in that the hard coat is The cloth film (A) has a hard coat layer (a2) on the side of at least one side of the resin film (a1) having a thickness of 130 μm or more, and the Vickers indenter having an inter-angle angle of 136° is loaded. 1 mN was pressed into the surface of the hard coat layer (a2) and measured to have a Martens' hardness of 250 N/mm ² or more. The protective adhesive film of claim 1, wherein the hard coat layer (a2) has a thickness of from 3 μm to 25 μm. For example, in the protective adhesive film of claim 1 or 2, wherein the adhesive layer (B) has a dynamic viscoelastic spectrum at a frequency of 1 Hz, and the storage elastic modulus at 20 ° C is 1.0 × 10 ⁵ Pa~ 5.0 × 10 ⁵ Pa. The protective adhesive film according to claim 1 or 2, wherein the pencil hardness measured from the side of the hard coat layer (a2) of the hard coat film (A) is 3H or more. A laminate obtained by laminating a protective adhesive film and a polarizing plate according to any one of claims 1 to 4. An information display device having a configuration in which a protective adhesive film according to any one of claims 1 to 4 is attached to at least one surface of a polarizing plate having a thickness of 50 μm to 200 μm. A portable electronic terminal device having a structure in which a protective adhesive film according to any one of claims 1 to 4 is attached to at least one surface of a polarizing plate having a thickness of 50 μm to 200 μm.