JP6503817B2 - Hard coat film and information display device - Google Patents

Description

  The present invention relates to a hard coat film that can be used by being attached to the surface of an information display device such as a liquid crystal panel or an EL display.

  A further reduction in weight and thickness is required for portable electronic terminals such as mobile personal computers, electronic organizers, and mobile phones. In connection with it, weight reduction and thickness reduction are calculated | required also for the information display apparatus installed in the said portable electronic terminal.

  As the information display device, a device having a configuration in which a liquid crystal module having a touch panel function called a so-called on-cell type or in-cell type and a polarizing plate are laminated has been developed.

  However, the information display device has a configuration of a liquid crystal module due to a strong impact that may occur when a dent or damage to the polarizing plate or the like is caused by a pressure that may occur during touch input, or when a portable electronic terminal is dropped or the like. It could cause damage to the glass panel used as a member.

  As a method of preventing damage to the polarizing plate by the pressure, damage to the glass panel constituting the liquid crystal module by strong impact, etc., for example, a glass substrate is provided on the surface side of the polarizing plate, and the surface of the glass substrate The method of providing a hard coat film is known (for example, refer patent document 1).

  However, the glass substrate is relatively expensive, and a portable electronic terminal or the like obtained using the glass substrate is thick and heavy, so it can not cope with the reduction in thickness and weight required by the industry. was there.

  As an information display apparatus which made the said weight reduction and thickness reduction compatible, what provided the conventional hard-coat film directly on surfaces, such as a polarizing plate, is mentioned, for example.

  However, even when the portable electronic terminal and a hard key such as a key are put together in a pocket etc., a very high level of scratch resistance which does not cause abrasion etc. is the case. Among electronic terminals, portable electronic terminals provided with an information display device having a conventional configuration suffer from abrasion caused by repeated contact of the keys and the like, and as a result, appearance defects of the hard coat film are caused. There was a case.

JP, 2008-095064, A

  The problem to be solved by the present invention is to provide a hard coat film with very excellent scratch resistance.

  The present invention is a hard coat film having a hard coat layer (a1) on at least one surface side of a substrate, wherein the hard coat layer (a1) is a compound having a double bond equivalent of less than 105 g / mol ((1) a1-1) Hard coat film which is a layer formed using a hard coat agent containing 50 mass% or more and a compound (a1-2) having a double bond equivalent of 105 g / mol or more and 200 g / mol or less Solve the above problems.

  The hard coat film of the present invention has very excellent scratch resistance, and can be used for the purpose of surface protection of information display devices such as liquid crystal displays and organic EL displays.

  In the hard coat film of the present invention, among the hard coat films having the hard coat layer (a1) on at least one surface side of the substrate, the hard coat layer (a1) has a double bond equivalent of less than 105 g / mol. It has a layer formed using a hard coating agent containing 50% by mass or more of the compound (a1-1) and the compound (a1-2) having a double bond equivalent of 105 g / mol or more and 200 g / mol or less It is characterized by being.

  By forming the specific hard coat layer (a1), it is possible to impart very excellent scratch resistance.

  The hard coat layer (a1) is a compound (a1) having 50% by mass or more of a compound (a1-1) having a double bond equivalent of less than 105 g / mol and a double bond equivalent of 105 to 200 g / mol. It can form by using the hard-coat agent containing-2).

  As the compound (a1-1), for example, a compound having a double bond equivalent of less than 105 g / mol is used. The double bond equivalent is a value obtained by dividing the molecular weight of the compound by the number of moles of the double bond group (CH2 = CH-) possessed by one molecule of the compound [molecular weight of compound / double dose possessed by one compound molecule] The number of moles of bonding group] (g / mol) is represented.

  The compound (a1-1) has a double bond equivalent of 70 g / mol or more and less than 105 g / mol in order to further improve the durability such as the scratch resistance of the hard coat layer (a1). Is preferably used, more preferably 80 g / mol or more and less than 105 g / mol, and still more preferably 85 g / mol or more and 103 g / mol or less.

  Further, the compound (a1-1) is used in an amount of 50% by mass or more based on the total amount of the solid content of the hard coat agent. Thereby, a hard coat film with very excellent scratch resistance can be obtained.

  The compound (a1-1) is preferably used in a range of 50% by mass to 95% by mass with respect to the total amount of solids contained in the hard coat agent forming the hard coat layer (a1), 60 mass It is more preferable to use in the range of% to 95% by mass, and it is particularly preferable to use in the range of 70% by mass to 95% by mass in order to obtain a hard coat film with further excellent scratch resistance.

  As said compound (a1-1), polyfunctional (meth) acrylate (X) which is a compound which has a 3 or more (meth) acryloyl group in a molecule | numerator, for example can be used.

  As the polyfunctional (meth) acrylate (X), for example, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane Tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri ( Meta) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Ruhekisa etc. (meth) acrylate, it can be combined used alone or two or more.

  The multifunctional (meth) acrylate (X) has a double bond equivalent of less than 105 g / mol as described above in order to further improve the durability such as the scratch resistance of the hard coat layer (a1). It is preferable to use one, more preferably in the range of 70 g / mol or more and less than 105 g / mol, still more preferably 80 g / mol or more and less than 105 g / mol, and more preferably 85 g / mol or more It is particularly preferred to use those of 103 g / mol or less.

  As polyfunctional (meth) acrylates having a double bond equivalent in the above range, pentaerythritol tetraacrylate (double bond equivalent: 88.0 g / mol), pentaerythritol triacrylate (double bond equivalent: 99.3 g / mol) And dipentaerythritol hexaacrylate (double bond equivalent: 96.3 g / mol), dipentaerythritol pentaacrylate (double bond equivalent: 102.0 g / mol), etc., and dipentaerythritol hexaacrylate and dipentaerythritol It is preferred to use pentaacrylate.

  Further, as the compound (a1-1), a compound (a1-1-1) having a double bond equivalent of 100 g / mol or less and a hydroxyl group having a double bond equivalent of more than 100 g / mol and less than 105 g / mol It is preferable to obtain a hard coat film further excellent in abrasion resistance by combining and using the compound (a1-1-2).

  Examples of the compound (a1-1-1) include pentaerythritol tetraacrylate (double bond equivalent: 88.0 g / mol) and pentaerythritol triacrylate (double bond equivalent: 99.3 g / mol) dipentaerythritol hexaacetate. Acrylate (double bond equivalent: 96.3 g / mol) or the like can be used, and in particular, dipentaerythritol hexaacrylate (double bond equivalent: 96.3 g / mol) is preferable.

  The compound (a1-1-1) is preferably used in the range of 40% by mass to 80% by mass, and is used in the range of 40% by mass to 70% by mass with respect to the solid content of the hard coat agent. Is more preferable, and it is further preferable to use in the range of 45% by mass to 70% by mass.

  Moreover, as said compound (a1-1-2), a dipentaerythritol pentaacrylate (double bond equivalent: 102.0 g / mol) etc. can be used, for example.

  It is preferable to use the said compound (a1-1-2) in 10 mass%-40 mass% with respect to solid content of the said hard-coat agent, and using in 15 mass%-40 mass% Is more preferably used in the range of 20% by mass to 40% by mass, and it is particularly preferable to use in the range of 20% by mass to 35% by mass in order to obtain further excellent scratch resistance.

  Further, the mass ratio [(a1-1-1) / (a1-1-2)] of the compound (a1-1-1) and the compound (a1-1-2) is the plastic hardness of the above-mentioned range In order to form a hard coat film having a hardness and to further improve the durability such as the scratch resistance of the hard coat layer (a1), the range of 50/50 to 90/10 is preferable, 55/90. The range of 45 to 90/10 is more preferable, and the range of 60/40 to 90/10 is more preferable.

  Further, as the hard coat layer (a1), a hard coat agent containing a combination of a compound (a1-2) having a double bond equivalent of 105 g / mol or more and 200 g / mol or less together with the compound (a1-1) It is preferable to use a hard coat layer obtained by using the above to obtain a hard coat film further excellent in abrasion resistance.

  As the compound (a1-2), for example, a compound (a1-2-1) having a (meth) acryloyl group and a urethane bond is preferably used, and various urethane (meth) acrylates are more preferably used. It is preferable to use urethane (meth) acrylate having two or more (meth) acryloyl groups in the molecule, and use of urethane (meth) acrylate having four or more (meth) acryloyl groups in the molecule More preferably, using urethane (meth) acrylate having five or more (meth) acryloyl groups in the molecule suppresses curing shrinkage of the hard coating agent and is excellent in high surface hardness and durability. It is particularly preferable to form a hard coat layer.

  In addition, as the urethane (meth) acrylate, it is easy to suppress the aggregation and crystallization of the resin before forming the coating film, and for example, to easily suppress point defects related to the appearance quality after forming the coating film, fat It is preferable to use a group urethane (meth) acrylate, and it is more preferable to use a so-called chain aliphatic urethane (meth) acrylate having no aromatic structure or aliphatic cyclic structure.

  It is preferable to use what is obtained by, for example, making polyisocyanate and (meth) acrylate which has a hydroxyl group react, as compounds (a1-2-1), such as said urethane (meth) acrylate.

  Examples of the polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), and 1,3-bis (isocyanatomethyl) cyclohexane; Alicyclic polyisocyanates such as 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane and the like can be used.

  As said polyisocyanate, the trimer of the said aliphatic polyisocyanate or alicyclic polyisocyanate can also be used.

  As the polyisocyanate, hexamethylene diisocyanate which is an aliphatic diisocyanate, norbornane diisocyanate which is an alicyclic diisocyanate, and isophorone diisocyanate can be used to obtain a more excellent hard coat film having durability such as scratch resistance. Preferred.

  Examples of the (meth) acrylate having a hydroxyl group that can be used for producing the compound (a1-2-1) include, for example, trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane di (meth) acrylate, and propylene oxide Modified trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, bis ((meth) acryloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipenta An erythritol penta (meth) acrylate etc. can be used individually or in combination of 2 or more types.

  Among them, using a pentaerythritol tri (meth) acrylate or a dipentaerythritol penta (meth) acrylate as the hydroxyl group-containing (meth) acrylate is a hard coat layer which is further excellent in durability such as scratch resistance. It is preferable to obtain a hard coat film provided with

  The compound (a1-2-1) can be produced by subjecting the polyisocyanate and the (meth) acrylate having a hydroxyl group to a urethanation reaction in the presence of a urethanization catalyst in a conventional manner.

  Examples of the urethanization catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin Examples thereof include organic tin compounds such as diacetate and tin octylate, and organic zinc compounds such as zinc octylate.

  The compounds (a1-2-1) obtained by the above method can be used alone or in combination of two or more.

  The compound (a1-2) is preferably contained in an amount of 5% by mass to 50% by mass, and more preferably 5% by mass to 40% by mass, with respect to the solid content of the hard coat agent. A content of 5% by mass to 30% by mass is more preferable in order to obtain a hard coat film having a still higher surface hardness and excellent durability such as scratch resistance.

  The mass ratio [(a1-1) / (a1-2)] between the compound (a1-1) and the compound (a1-2) makes the durability such as the scratch resistance of the hard coat layer (a1) more In order to further improve, it is preferably in the range of 95/5 to 50/50, more preferably in the range of 95/5 to 60/40, and in the range of 95/5 to 70/30. The range is more preferably 90/10 to 75/25.

  The total amount of the compound (a1-1) and the compound (a1-2) used is based on 100 parts by weight of the solid content of the hard coating agent to obtain a hard coat film having higher scratch resistance. 70.0 parts by mass to 99.95 parts by mass, more preferably 75.0 parts by mass to 99.5 parts by mass, and 80.0 parts by mass to 99.5 parts by mass Is more preferred.

  Moreover, as a hard-coat agent which can be used for formation of the said hard-coat layer (a1), it has one (meth) acryloyl group in molecule | numerator in the range which does not impair the effect of this invention other than what was mentioned above. It is possible to use those containing other (meth) acrylates such as mono (meth) acrylate and di (meth) acrylate having two (meth) acryloyl groups in the molecule. The amount thereof to be used is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, based on 100 parts by mass in total of the compound (a1-1) and the compound (a1-2). .

  Active energy ray curable composition comprising the compound (a1-1) contained in the hard coat agent, the compound (a1-2), and an active energy ray curable compound (Z) which can be used if necessary The total double bond equivalent of is preferably in the range of 95 g / mol to 130 g / mol, more preferably in the range of 95 g / mol to 120 g / mol, in the range of 95 g / mol to 115 g / mol It is further preferable to obtain a hard coat film having even better scratch resistance.

  As a hard-coating agent which can be used for formation of the said hard-coat layer (a1), what contains the photoinitiator which can start a hardening reaction can be used by irradiating an active energy ray.

  Examples of the photopolymerization initiator include an intramolecular cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo [2-hydroxy-2-methyl-1- [4- ( 1-Methylvinyl) phenyl] propanone], benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy) 2-Propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Acetophenone compounds such as butanone; benzoin, benzoin methyl ether, ben Benzoin such as isopropyl ether; acyl phosphine oxide compounds such as 2,4,6-trimethylbenzoin diphenyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide; benzyl, methyl phenyl glyoxy ester, etc. Can be mentioned.

  On the other hand, as a hydrogen abstraction type photopolymerization initiator, for example, benzophenone, methyl 4-phenylbenzophenone o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide Acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone Benzophenone series compounds such as; 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, thioxanthone type compounds such as 2,4-diethyl thioxanthone, 2,4- dichloro thioxanthone etc .; Mihula-ketone, 4,4'-die Aminobenzophenone compounds such as lamino benzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1- [4- (4-benzoylphenylsulfanyl) And the like.) Phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one and the like. These photopolymerization initiators can be used alone or in combination of two or more.

  Moreover, as said hard-coat agent, what contains a photosensitizer can be used.

  Examples of the photosensitizer include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine, urea compounds such as o-tolylthiourea, sodium diethyl dithiophosphate, and s-benzylisothyuronium-p-toluene. And sulfur compounds such as sulfonates.

  The amount of the photopolymerization initiator and the photosensitizer used is preferably 0.05 parts by mass to 20 parts by mass with respect to 100 parts by mass of the non-volatile component of the hard coat agent, and is preferably 0.5 parts by mass More preferably, it is 10 parts by mass. In the case of using ionizing radiation such as electron beam, alpha ray, beta ray, and gamma ray as the active energy ray, it is not necessary to use a photopolymerization initiator or a photosensitizer.

  The hard coating agent may be diluted with an appropriate solvent.

  Examples of the solvent include acetone, isobutyl alcohol, 2-propanol, isopentyl alcohol, ethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-normal-butyl ether, ethylene glycol monomethyl ether, ortho -Dichlorobenzene, xylene, cresol, chlorobenzene, isobutyl acetate, isopropyl acetate, isopentyl acetate, ethyl acetate, normal-butyl acetate, normal-propyl acetate, normal-propyl acetate, normal-pentyl acetate, methyl acetate, cyclohexanol, cyclohexanone, 1,4 -Dioxane, dichloromethane, N, N-dimethylformamide, styrene, tetrachloroethylene, tetrahydrofuran, 1,1,1 Trichloroethane, toluene, n-hexane, 1-butanol, 2-butanol, methanol, methyl isobutyl ketone, methyl ethyl ketone, methyl cyclohexanol, methyl cyclohexanone, methyl - n - butyl ketone, and the like. These solvents may be used alone or in combination of two or more.

  As the hard coating agent, various antifouling agents can be used for the purpose of imparting the sliding property and the staining resistance and the like of the surface of the hard coating layer (a1).

  As the anti-soiling agent, any of the conventionally known ones can be used, but in order to further improve the sliding property and the stain resistance of the surface of the hard coat layer (a1), an active energy ray-curable having fluorine atoms and silicon atoms An antifouling agent containing the compound (Z) can be used.

  As the active energy ray curable compound (Z) having a fluorine atom and a silicon atom, for example, among compounds having a fluorocarbon chain, a siloxane chain, or a hydrocarbon chain, those having a fluorine atom and a silicon atom are used can do.

  Specifically, it is preferable to use one having a poly (perfluoro alkylene ether) chain as a fluorocarbon chain and having a cyclopolysiloxane structure, and a bivalent group at each end of the poly (perfluoro alkylene ether) chain. It is preferable to use a compound (z1) having a structure in which a cyclopolysiloxane structure is bonded via the linking group of (1) and a (meth) acryloyl group is bonded to the cyclopolysiloxane structure via the divalent linking group.

  As a poly (perfluoro alkylene ether) chain which the said compound (z1) has, what has the structure which the C1-C3 bivalent fluorocarbon group and oxygen atom were connected alternately is mentioned. The divalent fluorocarbon group having 1 to 3 carbon atoms may be one kind or a combination of two or more kinds, and specifically, those represented by the following general formula (1) It can be mentioned.

(In the above general formula (1), X is one of the following formulas (1-1) to (1-5), and X is any one of the following formulas (1-1) to (1-5) In addition, two or more of the following formulas (1-1) to (1-5) may be present in random or block form, and n is a repeating unit. Is an integer of 2 to 200.)

  Among the poly (perfluoro alkylene ether) chains, among the above, a perfluoromethylene group represented by the formula (1-1) and a perfluoroethylene group represented by the formula (1-2) It is preferable that it is a poly (perfluoro alkylene ether) chain comprised by these, in order to improve stain resistance and slipperiness.

  The molar ratio of the perfluoromethylene group represented by the formula (1-1) to the perfluoroethylene group represented by the formula (1-2) [perfluoro represented by the formula (1-1) The methylene group / perfluoroethylene group represented by the above formula (1-2) is preferably in the range of 1/10 to 10/1. The value of n in the general formula (1) is preferably in the range of 2 to 200, more preferably in the range of 10 to 100, and still more preferably in the range of 20 to 80.

  As a cyclopolysiloxane structure which the said compound (z1) has, the structure represented by following General formula (2) is mentioned, for example.

(In the above general 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 has a (meth) acryloyl group. 1 And m is an integer of 2 to 5.)

  Among the cyclopolysiloxane structures described above, the cyclotetrasiloxane structure in which m in the general formula (2) is 3 is preferable among them.

  The divalent linking group for linking the poly (perfluoroalkylene ether) chain and the cyclopolysiloxane structure is not particularly limited as long as it is a divalent organic group, and is represented, for example, by the following general formula (3) Things are mentioned.

(In the said General formula (3), Y is a C1-C6 alkylene group.)

  Further, the divalent linking group for bonding the cyclopolysiloxane structure and the (meth) acryloyl group is not particularly limited as long as it is a divalent organic group, and is represented by, for example, the following general formula (4) The thing is mentioned.

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

The compound (z1) can be produced, for example, through the following steps (1) to (3).
(1) A compound having an allyl group at both ends of a poly (perfluoroalkylene ether) chain and a cyclopolysiloxane compound having a hydrosilyl group are reacted in the presence of a platinum-based catalyst to obtain both poly (perfluoroalkylene ether) chains Obtaining a compound having a cyclopolysiloxane structure at an end.
(2) A step of reacting the compound obtained in the above (1) with an allyloxyalkanol in the presence of a platinum catalyst, and adding a hydroxyl group to the cyclopolysiloxane structural moiety of the compound obtained in (1).
(3) A step of reacting a (meth) acrylate having an isocyanate group with the hydroxyl group added in (2) to introduce a (meth) acryloyl group.

  The active energy ray curable compound (Z) such as the compound (z1) obtained by the above method is contained in the range of 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the solid content of the hard coating agent It is preferable to be contained in the range of 0.1 parts by mass to 2 parts by mass in order to achieve both of the more excellent surface hardness and the stain resistance.

  In addition, as the hard coating agent, if necessary, a polymerization inhibitor, a surface conditioner, an antistatic agent, an antifoaming agent, a viscosity regulator, a light resistance stabilizer, a weathering stabilizer, a heat resistance stabilizer, an ultraviolet light absorber, Additives such as antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, silica beads, organic beads, etc .; and inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, antimony pentoxide, etc. Can be used.

  The hard coat film of the present invention can be produced, for example, by applying and curing the hard coat agent on at least one surface of a substrate to form a hard coat layer (a1).

  Examples of the method for applying the hard coat agent to the substrate include gravure coat, roll coat, comma coat, air knife coat, kiss coat, spray coat, cross coat, dip coat, spinner coat, wheel coat, brush coat, Examples of the method include coating by silk screen such as beta coat, wire bar coat, flow coat, etc., and printing methods such as offset printing method and letterpress printing method.

  Among the methods described above for applying the hard coating agent to the substrate, it is possible to adopt methods such as gravure coating, roll coating, comma coating, air knife coating, kiss coating, wire bar coating, flow coating, etc. It is preferable to form a hard coat layer (a1) of uniform thickness.

  As a method of curing the hard coat agent, for example, when the hard coat agent contains an active energy ray curable composition, the active energy ray is applied to the coated surface obtained by applying and drying the hard coat agent. There is a method of curing.

  Examples of the active energy ray include ionizing radiation such as ultraviolet ray, electron beam, alpha ray, beta ray, and gamma ray.

  As an apparatus which irradiates the said active energy ray, if it is an ultraviolet-ray, for example, the low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), a chemical lamp, a black light as the generation source A lamp, a mercury-xenon lamp, a short arc lamp, a helium-cadmium laser, an argon laser, sunlight, an LED and the like can be mentioned.

  When forming a hard-coat layer (a1) by irradiating the said ultraviolet-ray, it is preferable to perform irradiation of the said ultraviolet-ray under inert gas atmosphere, such as nitrogen gas, in order to suppress oxygen inhibition of radical polymerization.

  In addition to the irradiation of the active energy ray, if it can be heated, the active energy ray may be irradiated and then heated if necessary, and after the heating, the active energy ray may be irradiated. You may

  Examples of the substrate that can be used when producing the hard coat film include, for example, polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, polyethylene film, polypropylene film, cellophane film, diacetyl cellulose film, triacetyl cellulose film , Acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, Polyether sulfone film, polyether imide film, polyimide Irumu, fluorine resin film, nylon film, it is possible to use an acrylic resin film or the like.

  As the substrate, using one having an elastic modulus in the range of 3 GPa to 15 GPa makes it easy to suppress the warpage of the hard coat film, and effectively suppress the decrease in the surface hardness of the hard coat film. It is preferable because Moreover, since the hard coat film obtained using the base material having the elastic modulus in the above range is relatively soft, the hard coat film may be used as the curved surface, for example, on a adherend having a gently curved surface portion or the like. It is preferable because it can be stuck along the part.

  It is preferable to use a highly transparent substrate as the substrate, since good visibility can be ensured even when the hard coat film is installed on the surface of the display of the information display device. The total light transmittance of the substrate is preferably 85% or more, more preferably 88% or more, and particularly preferably 90% or more.

  As the substrate, for the purpose of further improving the adhesion to the hard coat layer (a1), those provided with a primer layer can be used.

  In addition, as the substrate, the surface is roughened by a sand blast method, a solvent treatment method, or the like for the purpose of further improving the adhesion to the hard coat layer (a1) and the adhesive layer (a3) described later. It is possible to use those subjected to surface treatment such as treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet irradiation treatment, oxidation treatment and the like.

  Among the resin films, a resin film containing an antistatic agent or the like can be used as the substrate.

  Examples of the antistatic agent include, as nonionic, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol, polyoxyethylene alkyl amine, polyoxyethylene alkyl amine, fatty acid polyethylene glycol ester, fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, Examples include fatty acid glycerin esters, alkyl polyethylene imines and the like. As a cationic system, alkylamine salts, alkyl quaternary ammonium salts, alkyl imidazoline derivatives and the like can be mentioned. Further, acrylate compounds having ethylene oxide as a skeleton can also be used. As the conductive polymer, polyaniline, polypyrrole, polythiophene, poly3,4-ethylenedioxythiophene and derivatives thereof can be used. Antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), aluminum-doped zinc oxide, antimony suboxide and the like can be used as the metal oxide. In addition, an ion conduction type antistatic agent which mixes metal ions such as lithium ions can also be used.

  As the substrate, it is preferable to appropriately select and use a substrate capable of suppressing the warpage of the hard coat film accompanying the curing shrinkage of the hard coat layer (a1) in order to prevent the excessive warpage of the hard coat film .

  Specifically, as the substrate, a substrate having a thickness of 130 μm or more is preferably used, and a substrate having a thickness of 130 μm to 300 μm is more preferably used, and a thickness of 150 μm to 250 μm is used. It is more preferable to use a certain one because it is possible to achieve both suppression of the warpage of the hard coat film and very excellent abrasion resistance and to contribute to the reduction in thickness and weight of the final product such as a portable electronic terminal.

  The hard coat layer (a1) formed on one side or both sides of the substrate preferably has a thickness of 3 μm to 25 μm, more preferably 5 μm to 20 μm, and still more preferably 7 μm to 16 μm. It is more preferable that the hard coat film having the above-mentioned range is obtained because a hard coat film with a further excellent scratch resistance and a hard coat film with an adhesive layer can be obtained without causing excessive warpage of the hard coat film.

  As an embodiment of the hard coat film of the present invention obtained by the above method etc., the hard coat film (a1) is provided on one side or both sides of the substrate directly or through another layer It can be used.

  The hard coat film preferably has a total thickness of 135 μm to 400 μm, more preferably 150 μm to 350 μm, and more preferably 150 μm to 300 μm. It is preferable that the abrasion resistance of the polarizing plate and the like can be prevented from being scratched, and the reduction in thickness and weight of the final product such as a portable electronic terminal can be achieved.

As the hard coat film, one having a plastic hardness of 2000 N / mm ² or more, which is measured by pressing a Vickers indenter having a space angle of 136 ° into the surface of the hard coat layer (a1) with a load of 1 mN, is used. it is ^preferred, preferably in the range of ^{2000N / mm 2 ~5000N / mm 2} , more preferably in the range of ^{2000N / mm 2 ~4500N / mm 2} , in the range of 2000N / mm ² ~4000N / mm 2 It is preferable to maintain the scratch resistance more excellent and to suppress the crack of the hard coat layer which may occur at the time of cutting and processing.

  Here, the plastic hardness is obtained by bonding the surface of the hard coat film of the present invention not having the hard coat layer (a1) to a glass panel via a pressure-sensitive adhesive layer having a thickness of 25 μm. And a Vickers indenter with an inter-peak angle of 136 ° pressed into the surface of the hard coat layer (a1) with a load of 1 mN. Further, among the hard coat films of the present invention, the plastic hardness of the hard coat film having the hard coat layer (a1) on both sides of the substrate is 25 μm in thickness of one of the sides and the glass panel. The adhesive was used as a test piece, and a Vickers indenter with an inter-peak angle of 136 ° was pressed into the surface of the hard coat layer (a1) with a load of 1 mN to indicate the measured value.

  Further, as the hard coat film, it is preferable to use one having an arithmetic mean roughness Ra of the surface of the hard coat layer (a1) of 0 μm to 0.5 μm, and is in the range of 0 μm to 0.3 μm. Is more preferable, and the range of 0 μm to 0.1 μm is more preferable in order to obtain higher abrasion resistance.

  In addition, when forming a hard coat layer having an arithmetic average roughness in the above range, the content of particulate matter in the hard coat layer (a1) is 0 mass to the entire hard coat layer (a1) It is preferable to adjust so as to be in the range of 50% by mass, and it is more preferable to adjust so as to be in the range of 0% by mass to 40% by mass, so as to be in the range of 0% by mass to 30% by mass It is more preferable to adjust, and it is adjusted to be in the range of 0% by mass to 20% by mass. For example, a portable electronic terminal or the like to which the hard coat film is attached is repeatedly contacted with a hard object such as a key. It is particularly preferable in order to prevent scratching on the surface of the hard coat layer to cause appearance defects.

  Further, as the hard coat film, it is preferable to use one having a pencil hardness of 2H or more on the surface of the hard coat layer (a1) constituting the hard coat film, and to use one having 3H or more, Even when the pressure-sensitive adhesive layer (a3) is laminated on the hard coat film to form a hard coat film with a pressure-sensitive adhesive layer, the decrease in surface hardness can be suppressed, and as a result, the adherend such as the polarizing plate It is preferable because damage and abrasion of the hard coat film itself can be effectively prevented.

  Moreover, as the hard coat film of the present invention, one provided with an adhesive layer (a3) on one side thereof can be used.

  As the pressure-sensitive adhesive layer (a3), it is preferable to use one having a suitable adhesion to an adherend such as a polarizing plate and having excellent transparency.

  As the pressure-sensitive adhesive layer (a3), one having a thickness in the range of 5 μm to 150 μm is preferably used, and one having a thickness in the range of 10 μm to 100 μm is more preferably used, 15 μm to 50 μm The use of one having a thickness in the range of 1 has a suitable adhesive force to an adherend such as a polarizing plate, and a pressure such as a touch input from the surface side of the hard coat layer (a1) Even when it is received, it is preferable from the viewpoint of obtaining a hard coat film having a surface hardness high enough to prevent a depression such as a polarizing plate.

  Although the thickness of the pressure-sensitive adhesive layer (a3) is preferably relatively thick in view of improving the adhesive strength, the pencil hardness of the hard coat film with the pressure-sensitive adhesive layer tends to decrease accordingly . However, in the case of the hard coat film with pressure-sensitive adhesive layer of the present invention, even when a relatively thick pressure-sensitive adhesive layer is provided, its pencil hardness is not reduced, so high hardness and excellent adhesion and Can be compatible.

The pressure-sensitive adhesive layer (a3) is preferably a storage elastic modulus at 20 ° C. in the dynamic viscoelasticity spectrum at frequency 1Hz is ^{1.0 × 10 5 Pa~5.0 × 10 5} Pa, 1. more preferably 5 × a ^{10 5 Pa~4.5 × 10 5 Pa,} 2.0 × 10 5 Pa~4.0 be × ¹⁰ 5 Pa is a high hard coat film pressure-sensitive adhesive layer surface The hardness can be maintained, and for example, even when local pressure is generated on the surface of the hard coat film with an adhesive layer due to touch input or impact, alleviation of damage to adherends such as a polarizing plate It is further preferable because it can effectively prevent deformation and denting of the polarizing plate and the like.

  The pressure-sensitive adhesive layer (a3) can be formed by applying a pressure-sensitive adhesive or the like, or by laminating a double-sided pressure-sensitive adhesive tape, or the like. As the pressure-sensitive adhesive, acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives and the like can be used.

  Among them, as the pressure-sensitive adhesive, it is preferable to use an acrylic pressure-sensitive adhesive containing an acrylic polymer, because the adhesion to the hard coat film, the transparency, the weather resistance and the like can be further improved.

  As the acrylic polymer, those obtained by polymerizing (meth) acrylic monomers can be used. Examples of the (meth) acrylic monomer include (meth) acrylates, and it is preferable to use those containing (meth) acrylates having an alkyl group having 2 to 14 carbon atoms.

  Examples of the (meth) acrylate having an alkyl group having 2 to 14 carbon atoms include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, n-hexyl Acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, isodecyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec -Butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate Rate, n- octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, isodecyl methacrylate, lauryl methacrylate.

  Among the above-mentioned (meth) acrylates, it is preferable to use an alkyl (meth) acrylate having an alkyl group having 4 to 9 carbon atoms, as described above, and an alkyl acrylate having an alkyl group having 4 to 9 carbon atoms It is more preferred to use

  As the alkyl acrylate having an alkyl group having 4 to 9 carbon atoms, n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, and ethyl acrylate are more preferable because they can easily ensure suitable adhesion. .

  The (meth) acrylate having an alkyl group having 2 to 14 carbon atoms is preferably used in a range of 90 parts by mass to 99 parts by mass with respect to 100 parts by mass of the total amount of the (meth) acrylic monomers, It is more preferable to use in the range of 90 parts by mass to 96 parts by mass because it is easy to secure a suitable adhesive force.

  As said acrylic polymer, what has polar groups, such as a hydroxyl group, a carboxyl group, and an amido group, can be used, for example.

  The acrylic polymer can be produced, for example, by polymerizing (meth) acrylic monomers containing (meth) acrylic monomers having polar groups such as hydroxyl groups, carboxyl groups and amide groups.

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

  As the (meth) acrylate monomer having a carboxyl group, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, dimer of acrylic acid or methacrylic acid, ethylene oxide modified succinic acid acrylate, etc. It can be mentioned. Among these, it is preferable to use acrylic acid.

  Examples of the (meth) acrylate monomer having an amide group include N-vinyl-2-pyrrolidone, N-vinylcaprolactam, acryloyl morpholine, acrylamide, N, N-dimethyl acrylamide, 2- (perhydrophthalimide-N) And -yl) ethyl acrylate and the like. Among these, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and acryloyl morpholine are preferably used.

  Examples of the other vinyl-based monomer having a polar group include vinyl acetate, acrylonitrile, maleic anhydride, itaconic anhydride and the like.

  The (meth) acrylic monomer having a polar group is used in the range of 0.1% by mass to 20% by mass with respect to the total amount of (meth) acrylic monomers used for the production of the acrylic polymer. Is preferably used, more preferably in the range of 1% by mass to 13% by mass, and in the range of 1.5% by mass to 8% by mass, the cohesion, holding power, and adhesiveness are in a suitable range. It is more preferable because it is easy to adjust.

  The weight average molecular weight of the acrylic polymer is preferably 400,000 to 1,400,000, and more preferably 600,000 to 1,200,000. By setting it as the said weight average molecular weight, it is easy to adjust adhesive force to a specific range, and when setting it as a protective adhesive film, it is easy to ease local pressure at the time of an impact, touch input, etc. suitably.

The weight average molecular weight can be measured by gel permeation chromatography (GPC). More specifically, it can measure and obtain | require on the following GPC measurement conditions with a polystyrene conversion value, using Tosoh Corp. "SC8020" as a GPC measuring device.
(GPC measurement conditions)
Sample concentration: 0.5 mass% (tetrahydrofuran solution)
Sample injection volume: 100 μL
Eluent: tetrahydrofuran (THF)
・ Flow rate: 1.0 mL / min
・ Column temperature (measurement temperature): 40 ° C
・ Column: "TSKgel GMHHR-H" manufactured by Tosoh Corporation
・ Detector: Differential refraction

  As the pressure-sensitive adhesive, in order to further increase the cohesion, it is preferable to use one containing a crosslinking agent in addition to the acrylic polymer and the like.

  As said crosslinking agent, an isocyanate type crosslinking agent, an epoxy-type crosslinking agent, a chelate type crosslinking agent etc. are mentioned, for example.

  It is preferable to use the said crosslinking agent in the range from which the gel fraction of the adhesive layer formed will be 25 mass%-85 mass%, and it uses it in the range which becomes 40 mass%-80 mass% in gel fraction. It is more preferable that, when used in a range of 50% by mass to 75% by mass, the decrease in surface pencil hardness when the protective adhesive film of the present invention is attached to an adherend such as a polarizing plate The adhesion can also be made sufficient. In the present invention, the gel fraction was obtained by immersing the pressure-sensitive adhesive layer after curing in toluene and measuring the mass after drying of the insoluble portion remaining after standing for 24 hours, and expressed as a percentage with respect to the original mass It is a thing.

  As the pressure-sensitive adhesive, one further containing a tackifying resin can be used in order to further increase the adhesive strength.

  It is preferable to use the said tackifying resin in 10 mass parts-60 mass parts with respect to 100 mass parts of said acrylic polymers. Furthermore, when importance is attached to adhesiveness, it is preferable to add in 20 mass parts-50 mass parts.

  As the pressure-sensitive adhesive, those containing known and commonly used additives other than those described above can be used.

  For example, when it is desired to improve the adhesion to a glass substrate or a metal member as the additive, a silane cup is used in a range of 0.001 parts by mass to 0.005 parts by mass with respect to 100 parts by mass of the adhesive. It is preferred to add a ring agent. Furthermore, if necessary, plasticizers, softeners, fillers, pigments, flame retardants and the like can be added as other additives.

  The pressure-sensitive adhesive layer-carrying hard coat of the present invention is produced by directly applying and drying the pressure-sensitive adhesive on at least one surface of the hard coat film produced by the above method to form a pressure-sensitive adhesive layer (a3) be able to.

  The hard coat film with a pressure-sensitive adhesive layer of the present invention is a pressure-sensitive adhesive obtained by applying the above-mentioned pressure-sensitive adhesive on the surface of a release liner in advance on at least one surface of the hard coat film produced by the above method It can be produced by transferring layer (a3).

  The hard coat film and the hard coat film with the pressure sensitive adhesive layer of the present invention are protected pressure sensitive adhesive films by adjusting the physical property value and thickness of the hard coat film and the pressure sensitive adhesive layer (a3) to a specific range and combining them. Even if local pressure is applied due to impact or touch input, the stress can be properly relieved, so it has impact resistance that can suppress damage to the adherend, and Since the surface hardness of the hard coat film with the pressure-sensitive adhesive layer is not impaired, high scratch resistance can be realized.

  The hard coat film and the hard coat film with pressure-sensitive adhesive layer of the present invention have high surface hardness. Specifically, the pencil hardness of the hard coat film in a state where the hard coat film and the hard coat film with the pressure-sensitive adhesive layer are attached to a glass plate is preferably 2H or more, more preferably 3H or more. Therefore, the hard coat film and the hard coat film with pressure-sensitive adhesive layer of the present invention can be suitably used mainly as a protective pressure-sensitive adhesive film of an image display portion of a portable electronic terminal and a protective pressure-sensitive adhesive film of various displays.

[Laminate]
The laminate of the present invention is a laminate of the hard coat film of the present invention, the hard coat film with an adhesive layer, and a polarizing plate. Although in the past there was a case where a glass substrate was used by being laminated with the polarizing plate, there was a problem that it could not be wound in a roll shape.

  Since the laminate uses a resin film instead of a conventional thick glass substrate, it can be wound into a roll or the like, and can be bonded to a polarizing plate by so-called roll-to-roll, so its production Efficiency can be improved more than before.

  As a polarizing plate used for this invention, the general thing which laminated | stacked the polarizer protective layer on both surfaces of the polarizer can be used normally.

  The polarizer can use what is obtained using polyvinyl alcohol-type resin. The polyvinyl alcohol-based resin can be produced by saponifying a polyvinyl acetate-based resin.

  A polarizer can be manufactured, for example, by adsorbing and orienting a dichroic dye on a formed polyvinyl alcohol resin film.

  Moreover, a polarizing plate can be manufactured by laminating | stacking polarizer protective layers, such as a triacetyl-cellulose film, on both surfaces of the polarizer obtained above through an adhesive bond layer.

  As the dichroic dye, iodine or a dichroic organic dye can be used. In order to dye a polyvinyl alcohol-type resin film with a dichroic dye, it can carry out by immersing the said polyvinyl alcohol-type resin film in the aqueous solution containing these pigment | dyes. In the case of using iodine as the dichroic dye, usually, a method of dyeing by immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide is adopted.

  The polarizer protective layer is not particularly limited, but it is preferable to use one obtained by using a resin having excellent transparency, on the assumption that it is used as a display material.

  Examples of the polarizer protective layer include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, poly Vinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, cycloolefin resin film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyether Imide film, polyimide film, fluorine resin film, nylon Irumu, acrylic resin film or the like.

  Moreover, when forming a polarizer protective layer in both surfaces of the said polarizer layer, it is possible to form the polarizer protective layer comprised from different resin in each surface. For example, a polarizer protective layer made of a triacetylcellulose film can be formed on one side of the polarizer layer, and a polarizer protective layer made of a cycloolefin resin film can be formed on the other side.

  As the polarizing plate, it is preferable to use one having a thickness of 50 μm to 200 μm because this can contribute to weight reduction and thickness reduction of the image display device and the portable electronic terminal.

[Information display device and portable electronic terminal]
The information display device of the present invention has a configuration in which, for example, an LCD module (liquid crystal display module) and the laminate such as a screen panel are fixed via a highly transparent adhesive tape.

  Since the said structure has a structure which consists of said laminated body, it is equipped with the very excellent abrasion resistance in the surface layer of an information display apparatus, and it is hard to produce the damage of the polarizing plate and LCD module which are produced by local stress. Therefore, it is preferable that the above-mentioned composition is adopted to a portable electronic terminal which is susceptible to local stress by falling or the like.

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

Synthesis Example 1: Synthesis of Urethane Acrylate (A1)
Alonix's M-403 [Toagosei Co., Ltd. product, dipentaerythritol hexaacrylate (hereinafter referred to as DP6A) and dipentaerythritol pentaacrylate (hereinafter referred to as Mixture of DP5A (abbreviated as DP5A), DP6A / DP5A (mass ratio) = 45/55, hydroxyl value 99 mg KOH / g 1309 parts by mass, dibutyltin diacetate 0.3 parts by mass, Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.) Antioxidant] 4.48 parts by mass, and methoquinone (Seiko Chemical Co., Ltd. product, polymerization inhibitor) 0.45 parts by mass were added, and the temperature was gradually raised while uniformly mixing.

When the temperature in the flask reaches 60 ° C., 184.8 parts by mass of Desmodur H (Sumitomo Bayer Urethane Co., Ltd., hexamethylene diisocyanate) is added, and then reacted at 80 ° C. for 5 hours to further add an isocyanate group A mixture of urethane acrylate (A1) and DP6A (urethane acrylate (A1) / DP6A (mass ratio) = 61/39, solid content: 100% by mass) by reaction until the infrared absorption spectrum of 2250 cm ^-1 shown is lost 1493.8 parts by mass were obtained.

Synthesis Example 2 Synthesis of Urethane Acrylate (A2)
Aloniix M-403 (made by Toagosei Co., Ltd., a mixture of DP6A and DP5A, DP6A / DP5A (mass ratio) = 45/55, hydroxyl value in a flask equipped with a stirrer, a gas inlet tube, a condenser and a thermometer 99 mg KOH / g 1309 parts by mass, dibutyl tin diacetate 0.78 parts by mass, SMILIZER BHT [Sumitomo Chemical Co., Ltd., antioxidant] 4.66 parts by mass, Metoquinone [Seiko Chemical Co., Ltd., polymerization inhibitor] After 0.47 parts by mass was added, the temperature was gradually raised while uniformly mixing.

When the temperature in the flask reaches 60 ° C., 244.2 parts by mass of isophorone diisocyanate (hereinafter abbreviated as “IPDI”) is added, and then reacted at 80 ° C. for 5 hours to further show 2250 cm ⁻¹ showing an isocyanate group. The reaction is carried out until the infrared absorption spectrum of the compound disappears, whereby a mixture of urethane acrylate (A2) and DP6A (urethane acrylate (A2) / DP6A (mass ratio) = 62/38, solid content 100 mass%) 1553.2 mass parts I got

Synthesis Example 3: Synthesis of Urethane Acrylate (A3)
Alonix's M-305 (manufactured by Toagosei Co., Ltd., pentaerythritol tetraacrylate (hereinafter abbreviated as PE4A) and pentaerythritol triacrylate (hereinafter PE3A) in a flask equipped with a stirrer, a gas inlet tube, a condenser and a thermometer Mixtures of PE4A / PE3A (mass ratio) = 40/60, hydroxyl value 112 mg KOH / g] 340.4 parts by mass, bis (acryloxyethyl) hydroxyethyl isocyanurate [hydroxyl value 129 mg KOH / g] 340. 4 parts by mass, 0.24 parts by mass of dibutyltin diacetate, 4.09 parts by mass of Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd., antioxidant), and methoquinone (manufactured by SEIKO, Ltd., polymerization inhibitor) 0.41 The mass part was added, and it heated up gradually, mixing uniformly.

When the temperature in the flask reaches 60 ° C., 137.9 parts by mass of IPDI are added, and the reaction is carried out at 80 ° C. for 5 hours, and the reaction is continued until the infrared absorption spectrum at 2250 cm ^-1 showing an isocyanate group disappears. As a result, 818.6 parts by mass of a mixture of urethane acrylate (A3) and PE4A (urethane acrylate (A3) / PE4A (mass ratio) = 84/16, solid content 100 mass%) was obtained.

Synthesis Example 4 Synthesis of Urethane Acrylate (A4)
Aloniix M-305 (made by Toagosei Co., Ltd., a mixture of PE4A and PE3A, PE4A / PE3A (mass ratio) = 40/60, hydroxyl value in a flask equipped with a stirrer, a gas inlet tube, a condenser and a thermometer 1121.8 parts by mass of 112 mg KOH / g, 0.62 parts by mass of dibutyltin diacetate, 3.73 parts by mass of Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd., antioxidant), and methoquinone [manufactured by Seiko Chemical Co., Ltd., polymerized Inhibitor] 0.37 parts by mass was added, and the temperature was gradually raised while uniformly mixing.

When the temperature in the flask reaches 60 ° C., 222.3 parts by mass of IPDI is added, and then the reaction is carried out at 80 ° C. for 5 hours, and then the reaction is continued until the infrared absorption spectrum of 2250 cm ^-1 showing an isocyanate group disappears. 1244.1 parts by mass of a mixture of urethane acrylate (A4) and PE4A (urethane acrylate (A4) / PE4A (mass ratio) = 67/33, solid content 100% by mass) was obtained.

Synthesis Example 5 Synthesis of Urethane Acrylate (A5)
Aloniix M-305 (made by Toagosei Co., Ltd., a mixture of PE4A and PE3A, PE4A / PE3A (mass ratio) = 40/60, hydroxyl value in a flask equipped with a stirrer, a gas inlet tube, a condenser and a thermometer 1121.8 parts by mass of 112 mg KOH / g, 0.62 parts by mass of dibutyltin diacetate, 3.68 parts by mass of Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd., antioxidant), and methoquinone [manufactured by Seiko Chemical Co., Ltd., polymerized Inhibitor] 0.37 parts by mass was added, and the temperature was gradually raised while uniformly mixing.

When the temperature in the flask reaches 60 ° C., 206.2 parts by mass of norbornene diisocyanate (hereinafter, abbreviated as “NBDI”) is added, and then reacted at 80 ° C. for 5 hours to further display 2250 cm ⁻ A mixture of urethane acrylate (A5) and PE4A (urethane acrylate (A5) / PE4A (mass ratio) = 67/33, solid content 100 mass%) 1228.0 by reacting until the infrared absorption spectrum of ^{No. 1} disappears. The mass part was obtained.

Synthesis Example 6: Synthesis of Urethane Acrylate (A6)>
Aloniix M-305 (made by Toagosei Co., Ltd., a mixture of PE4A and PE3A, PE4A / PE3A (mass ratio) = 40/60, hydroxyl value in a flask equipped with a stirrer, a gas inlet tube, a condenser and a thermometer 112 mg of KOH / g] 549.1 parts by mass, 0.1 parts by mass of dibutyltin diacetate, 0.6 parts by mass of Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd., antioxidant), methoquinone (manufactured by Seiko Co., Ltd., polymerized) Inhibitor: 0.1 parts by mass and 160 parts by mass of butyl acetate were added, and the temperature was gradually raised while uniformly mixing.

After the temperature in the flask reaches 60 ° C., 90.9 parts by mass of Desmodur H (Sumitomo Bayer Urethane Co., Ltd., hexamethylene diisocyanate, NCO% = 50% by mass) is added, and then 5 at 80 ° C. A mixture of urethane acrylate (A6) and PE4A [urethane acrylate (A6) / PE4A (mass ratio) = 66 / by reaction for ¹ hour and further reaction until the infrared absorption spectrum of 2250 cm ⁻¹ showing an isocyanate group disappears. 34, solid content 80 mass%] 800 mass parts were obtained.

Synthesis Example 7: Synthesis of Urethane Acrylate (A7)
Aloniix M-305 (made by Toagosei Co., Ltd., a mixture of PE4A and PE3A, PE4A / PE3A (mass ratio) = 40/60, hydroxyl value in a flask equipped with a stirrer, a gas inlet tube, a condenser and a thermometer 112 mg KOH / g] 242 parts by mass, methoquinone (Seiko Chemical Co., Ltd., polymerization inhibitor) 0.23 parts by mass, 0.13 parts by mass of dibutyltin dilaurate and 100 parts by mass of methyl ethyl ketone are charged, and 75 ° C. while blowing in air. After heating up to 90% by mass of hexamethylene diisocyanate (isocyanurate) (Desmodur N 3390 BA, manufactured by Sumika Bayer Urethane Co., Ltd., solid content 90% by mass, NCO%: 19.6% by mass) 107 parts by mass And the mixed solution of 50 mass parts of methyl ethyl ketone was dripped over 2 hours.

After completion of the dropwise addition, the mixture is reacted at 75 ° C. for 4 hours, and the mixture is further reacted until the infrared absorption spectrum at 2250 cm ⁻¹ showing the isocyanate group disappears, whereby a mixture of urethane acrylate (A7) and PE4A [urethane acrylate (A7) / PE4A (mass ratio) = 71/29, solid content 67.8 mass%] 499 mass parts was obtained.

Synthesis Example 6: Synthesis of Fluorine-Atom-Containing Compound (z-1) Solution
In a flask equipped with a stirrer and a condenser, 500 parts by mass of perfluoropolyether having allyl groups at both ends represented by the following formula (5) in a dry nitrogen atmosphere, 700 parts by mass of m-xylene hexafluoride, 361 parts by mass of tetramethylcyclotetrasiloxane was charged, and the temperature was raised to 90 ° C. while stirring. Here, 0.442 parts by mass of a chloroplatinic acid / vinylsiloxane complex toluene solution (containing 1.1 × 10 ⁻⁶ mol as platinum alone) was charged, and the mixture was stirred for 4 hours while maintaining the internal temperature at 90 ° C. or higher. After confirming that the allyl group in the raw material has disappeared in the ¹ H-NMR spectrum, the solvent and excess tetramethylcyclotetrasiloxane are distilled off under reduced pressure, and activated carbon treatment is carried out to obtain a compound represented by the following formula (6) As a colorless and transparent liquid, a perfluoropolyether compound was obtained.

(Wherein, m / n is 0.9, and the sum of m and n is 45 on average)

Under dry air atmosphere, 50 parts by mass of perfluoropolyether compound represented by the above formula (6), 7.05 parts by mass of 2-allyloxyethanol, 50 parts by mass of m-xylene hexafluoride and chloroplatinic acid / vinyl The toluene solution of the siloxane complex (0.0442 parts by mass (containing 1.1 × 10 ⁻⁷ mol as platinum alone) was mixed, and stirred at 100 ° C. for 4 hours. After confirming that the Si-H group has disappeared by ¹ H-NMR spectrum and infrared absorption spectrum, the solvent and excess 2-allyloxyethanol are distilled off under reduced pressure, and activated carbon treatment is carried out to obtain the following formula (7) The perfluoropolyether compound which is a pale yellow transparent liquid represented by

  In a dry air atmosphere, 50 parts by mass of the perfluoropolyether compound represented by the formula (7), 50 parts by mass of tetrahydrofuran and 9 parts by mass of 2-acryloyloxyethyl isocyanate were mixed and heated to 50 ° C.

  Next, 0.05 parts by mass of dioctyl tin laurate was added, and the mixture was stirred at 50 ° C. for 24 hours. After completion of heating, the mixture was evaporated under reduced pressure at 80 ° C. and 0.27 kPa to obtain a light yellow paste-like fluorine atom-containing compound (A-1) represented by the following formula (11). A mixed solvent of methyl ethyl ketone and methyl isobutyl ketone (methyl ethyl ketone / methyl isobutyl ketone = 1/3 (mass ratio)) is added to the fluorine atom containing compound (z-1) to obtain a fluorine atom containing compound having a solid content of 20% by mass (z -1) A solution was prepared.

Preparation Example 1: Preparation of Hard Coating Agent (HC1)
80 parts by mass of a mixture of DP6A and DP5A (DP6A / DP5A (mass ratio) = 65/35), 20 parts by mass of the mixture of urethane acrylate (A1) and DP6A obtained in Synthesis Example 1, fluorine atom-containing compound (z 1) 1.5 parts by mass of a solution and 4.5 parts by mass of a photopolymerization initiator ("IRGACURE 184" manufactured by BASF Japan Ltd., 1-hydroxycyclohexyl phenyl ketone) in a mixed solvent (ethyl acetate / methyl ethyl ketone (mass ratio) The hard coat agent (HC1) was obtained by adjusting the solid content to 40% by mass using = 50/50).

Preparation Example 2 Preparation of Hard Coating Agent (HC2)
70 parts by mass of a mixture of DP6A and DP5A (DP6A / DP5A (mass ratio) = 65/35), 30 parts by mass of a mixture of urethane acrylate (A1) and DP6A obtained in Synthesis Example 1, fluorine atom-containing compound (z 1) 1.5 parts by mass of a solution and 4.5 parts by mass of a photopolymerization initiator ("IRGACURE 184" manufactured by BASF Japan Ltd., 1-hydroxycyclohexyl phenyl ketone) in a mixed solvent (ethyl acetate / methyl ethyl ketone (mass ratio) The hard coat agent (HC2) was obtained by adjusting the solid content to 40% by mass using = 50/50).

Preparation Example 3 Preparation of Hard Coating Agent (HC3)
Except that 30 parts by mass of the mixture of urethane acrylate (A2) and DP6A obtained in Synthesis Example 2 were used instead of 30 parts by mass of the mixture of urethane acrylate (A1) and DP6A obtained in Synthesis Example 1 In a similar manner to Preparation Example 1, a hard coat agent (HC3) having a solid content of 40% by mass was obtained.

Preparation Example 4 Preparation of Hard Coating Agent (HC4)
Instead of using 30 parts by mass of the mixture of urethane acrylate (A1) and DP6A obtained in Synthesis Example 1, 30 parts by mass of the mixture of urethane acrylate (A3) and PE4A obtained in Synthesis Example 3 were used. A hard coat agent (HC4) with a solid content of 40% by mass was obtained in the same manner as in Preparation Example 1.

Preparation Example 5 Preparation of Hard Coating Agent (HC5)
Except that 30 parts by mass of the mixture of urethane acrylate (A4) and PE4A obtained in Synthesis Example 4 was used instead of 30 parts by mass of the mixture of urethane acrylate (A1) and DP6A obtained in Synthesis Example 1 A hard coat agent (HC5) having a solid content of 40% by mass was obtained in the same manner as in Preparation Example 1.

Preparation Example 6 Preparation of Hard Coating Agent (HC6)
Instead of using 30 parts by mass of the mixture of urethane acrylate (A1) and DP6A obtained in Synthesis Example 1, 30 parts by mass of the mixture of urethane acrylate (A5) and PE4A obtained in Synthesis Example 5 were used. A hard coat agent (HC6) with a solid content of 40% by mass was obtained in the same manner as in Preparation Example 1.

Preparation Example 7 Preparation of Hard Coating Agent (HC7)
100 parts by mass of a mixture of urethane acrylate (A1) and DP6A obtained in Synthesis Example 1, 1.5 parts by mass of a fluorine atom-containing compound (z-1) solution and a photopolymerization initiator (manufactured by BASF Japan Ltd. "IRGACURE 184" Hard coat by adjusting 4.5 parts by mass of 1-hydroxycyclohexyl phenyl ketone) to a solid content of 40% by mass using a mixed solvent (ethyl acetate / methyl ethyl ketone (mass ratio) = 50/50) An agent (HC7) was obtained.

Preparation Example 8 Preparation of Hard Coating Agent (HC8)
Instead of using 30 parts by mass of the mixture of urethane acrylate (A1) and DP6A obtained in Synthesis Example 1, 30 parts by mass of the mixture of urethane acrylate (A2) and DP6A obtained in Synthesis Example 2 were used. A hard coat agent (HC8) with a solid content of 40% by mass was obtained in the same manner as in Preparation Example 7.

Preparation Example 9 Preparation of Hard Coating Agent (HC9)
100 parts by mass of the mixture of urethane acrylate (A1) and DP6A obtained in Synthesis Example 1, 20 parts by mass of the mixture of urethane acrylate (A3) and PE4A obtained in Synthesis Example 3, fluorine atom containing compound (z-1 ) Mixed solution (ethyl acetate / methyl ethyl ketone (mass ratio) = 50) 1.5 parts by mass of a solution and 4.5 parts by mass of a photopolymerization initiator ("IRGACURE 184" manufactured by BASF Japan Ltd., 1-hydroxycyclohexyl phenyl ketone) The hard coat agent (HC9) was obtained by adjusting the solid content to be 40% by mass using / 50).

Preparation Example 10 Preparation of Hard Coating Agent (HC10)
100 parts by mass of the mixture of urethane acrylate (A2) and DP6A obtained in Synthesis Example 2, 20 parts by mass of the mixture of urethane acrylate (A3) and PE4A obtained in Synthesis Example 3, fluorine atom-containing compound (z-1 ) Mixed solution (ethyl acetate / methyl ethyl ketone (mass ratio) = 50) 1.5 parts by mass of a solution and 4.5 parts by mass of a photopolymerization initiator ("IRGACURE 184" manufactured by BASF Japan Ltd., 1-hydroxycyclohexyl phenyl ketone) The hard coat agent (HC10) was obtained by adjusting the solid content to be 40% by mass using / 50).

Preparation Example 11 Preparation of Hard Coating Agent (HC11)
100 parts by mass of a mixture of DP6A and DP5A (DP6A / DP5A (mass ratio) = 65/35), 1.5 parts by mass of a fluorine atom-containing compound (z-1) solution and a photopolymerization initiator (manufactured by BASF Japan Ltd.) Irgacure 184 ", 1-hydroxycyclohexyl phenyl ketone) by adjusting the solid content to be 40% by mass using a mixed solvent (ethyl acetate / methyl ethyl ketone (mass ratio) = 50/50) A hard coating agent (HC11) was obtained.

Preparation Example 12 Preparation of Hard Coating Agent (HC12)
100 parts by mass of a mixture of PE4A and PE3A (PE4A / PE3A (mass ratio) = 40/60), 1.5 parts by mass of a fluorine atom-containing compound (z-1) solution and a photopolymerization initiator (manufactured by BASF Japan Ltd.) Irgacure 184 ", 1-hydroxycyclohexyl phenyl ketone) by adjusting the solid content to be 40% by mass using a mixed solvent (ethyl acetate / methyl ethyl ketone (mass ratio) = 50/50) A hard coating agent (HC12) was obtained.

Preparation Example 13 Preparation of Hard Coating Agent (HC13)
62 parts by mass of a mixture of urethane acrylate (A6) and PE 4A obtained in Synthesis Example 6 (containing 32.7 parts by mass of urethane acrylate (A6) and 16.9 parts by mass of PE4A), obtained in Synthesis Example 7 Mixture of urethane acrylate (A7) and PE4A (including 18.3 parts by mass of urethane acrylate (A7) and 3.6 parts by mass of PE4A), a mixture of PE4A and PE3A (mass ratio PE4A / PE3A (mass ratio) ) = 40/60) 38 parts by mass, reactive colloidal silica ("MEK-AC-2140Z" manufactured by Nissan Chemical Industries, Ltd., methyl ethyl ketone dispersion having a solid content of 40% by mass) 287.5 parts by mass (reactive silica (solids) Min) 115 parts by mass), non-reactive colloidal silica ("MEK-ST40" manufactured by Nissan Chemical Industries, Ltd., 40 mass% solid content Thiyl ethyl ketone dispersion) 312.5 parts by mass (non-reactive silica (solid content) 125 parts by mass), photopolymerization initiator (IRGACURE 184 manufactured by BASF Japan Ltd., 1-hydroxycyclohexyl phenyl ketone) 10.9 Parts by mass and photopolymerization initiator ("IRGACURE 754" manufactured by BASF Japan Ltd., oxyphenylacetic acid 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid 2- (2-hydroxyethoxy) ethyl ester (A mixture thereof) and 1.6 parts by mass were uniformly stirred, and then diluted with methyl ethyl ketone to adjust the solid content to 40% by mass to obtain a hard coating agent (HC13).

Example 1
The hard coat agent (1) is coated on one side of a polyethylene terephthalate film (Cosmoshine A4300 manufactured by Toyobo Co., Ltd.) having a thickness of 188 μm and an elastic modulus of 5.1 GPa using a bar coater and dried at 80 ° C. for 90 seconds Thickness using a UV irradiation device (Fusion UV Systems Japan Ltd. “F450”, lamp: 120 W / cm, H bulb) under a nitrogen atmosphere and irradiating ultraviolet light with an irradiation light quantity of 0.25 J / cm ² A hard coat film provided with a hard coat layer of 12 μm was obtained.

  Next, ZB7011W-2 (manufactured by DIC Corporation, adhesive tape) is applied by pressure at 4 kg / cm to the surface of the hard coat film made of the polyethylene terephthalate film, followed by curing at 40 ° C. for 2 days. A pressure-sensitive adhesive layer-attached hard coat film (1) having a thickness of 225 μm was obtained.

(Example 2)
A hard coat film (2) with a pressure-sensitive adhesive layer having a thickness of 225 μm was obtained in the same manner as in Example 1 except that the hard coat agent (2) was used instead of the hard coat agent (1).

(Example 3)
A pressure-sensitive adhesive layer-attached hard coat film (3) having a thickness of 225 μm was obtained in the same manner as in Example 1 except that the hard coat agent (3) was used instead of the hard coat agent (1).

(Example 4)
A hard coat film (4) with a pressure-sensitive adhesive layer having a thickness of 225 μm was obtained in the same manner as in Example 1 except that the hard coat agent (4) was used instead of the hard coat agent (1).

(Example 5)
A hard coat film (5) with a pressure-sensitive adhesive layer having a thickness of 225 μm was obtained in the same manner as in Example 1 except that the hard coat agent (5) was used instead of the hard coat agent (1).

(Example 6)
A hard coat film (4) with a pressure-sensitive adhesive layer having a thickness of 225 μm was obtained in the same manner as in Example 1 except that the hard coat agent (6) was used instead of the hard coat agent (1).

(Example 7)
A pressure-sensitive adhesive layer-attached hard coat film (7) with a thickness of 221 μm was obtained in the same manner as in Example 1 except that the thickness of the hard coat layer was 8 μm.

(Example 8)
A pressure-sensitive adhesive layer-attached hard coat film (8) having a thickness of 221 μm was obtained in the same manner as in Example 1 except that the thickness of the hard coat layer was 15 μm.

(Example 9)
A pressure-sensitive adhesive layer-carrying hard coat film (9) with a thickness of 221 μm was obtained in the same manner as in Example 1 except that the thickness of the hard coat layer was 20 μm.

(Example 10)
A pressure-sensitive adhesive layer-attached hard coat film (10) having a thickness of 287 μm was obtained in the same manner as in Example 1 except that the thickness of the polyethylene terephthalate film (Cosmoshine A4300 manufactured by Toyobo Co., Ltd.) was 250 μm.

(Example 11)
Hard coat with an adhesive layer in the same manner as in Example 1 except that a polyethylene terephthalate film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm was used instead of the polyethylene terephthalate film having a thickness of 188 μm. The film (11) was obtained.

(Example 12)
Hard coat with an adhesive layer in the same manner as in Example 1 except that a polyethylene terephthalate film (Cosmoshine A4300 manufactured by Toyobo Co., Ltd.) having a thickness of 75 μm was used instead of the polyethylene terephthalate film having a thickness of 188 μm. The film (12) was obtained.

(Comparative example 1)
A hard coat film (11) with a pressure-sensitive adhesive layer having a thickness of 225 μm was obtained in the same manner as in Example 1 except that the hard coat agent (7) was used instead of the hard coat agent (1).

(Comparative example 2)
A hard coat film (12) with a pressure-sensitive adhesive layer having a thickness of 225 μm was obtained in the same manner as in Example 1 except that the hard coat agent (8) was used instead of the hard coat agent (1).

(Comparative example 3)
A hard coat film (13) with a pressure-sensitive adhesive layer having a thickness of 225 μm was obtained in the same manner as in Example 1 except that the hard coat agent (9) was used instead of the hard coat agent (1).

(Comparative example 4)
A hard coat film (14) with a pressure-sensitive adhesive layer having a thickness of 225 μm was obtained in the same manner as in Example 1 except that the hard coat agent (10) was used instead of the hard coat agent (1).

(Comparative example 5)
A hard coat film (15) with a pressure-sensitive adhesive layer having a thickness of 225 μm was obtained in the same manner as in Example 1 except that the hard coat agent (11) was used instead of the hard coat agent (1).

(Comparative example 6)
A hard coat film (16) with a pressure-sensitive adhesive layer having a thickness of 225 μm was obtained in the same manner as in Example 1 except that the hard coat agent (12) was used instead of the hard coat agent (1).

  The following evaluation was performed about the hard coat film obtained by the said Example and comparative example and the hard coat film with an adhesive layer. The obtained results are shown in Tables 1 and 2.

(Arithmetic mean roughness of hard coat layer surface)
The hard coat film with a pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was pasted onto a glass plate via the pressure-sensitive adhesive layer such that the hard coat layer was on top.

  Then, arithmetic mean roughness Ra of the surface of the said hard-coat layer was measured using Ryota system company make Vert scan (model number: R3300G, CCD camera: SONY HR-50 1/3). At the time of measurement, the objective lens 5 times, the wavelength filter 530 WHITE, and the measurement mode Wave were used.

(Plastic hardness)
The hard coat film with a pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was pasted onto a glass plate via the pressure-sensitive adhesive layer such that the hard coat layer was on top.

  Thereafter, Martens hardness of the surface of the hard coat layer was measured using Fisher scope HM 2000 X yp (Fisher Instruments Inc.) by pressing a Vickers indenter with an interpeak angle of 136 ° into a 1 mN load for 20 seconds.

(Water contact angle)
The hard coat film with a pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was pasted onto a glass plate via the pressure-sensitive adhesive layer such that the hard coat layer was on top.

  Next, using an automatic contact angle meter "DROMPAMSTER 500" manufactured by Kyowa Interface Science Co., Ltd., 3 μL of purified water was deposited on the surface of the hard coat layer, and then the contact angle after 1 second was measured. The method of calculating the contact angle in this measurement was the static drop method among the test methods described in JIS R3257.

(The appearance of the hard coat layer)
The hard coat films obtained in Examples and Comparative Examples were cut into 7 cm × 14 cm, and the number of point defects was visually counted and judged based on the following criteria.

  ◎: There was no point defect.

  ○: There was one point defect.

  X: Two or more point defects were present.

(Abrasion resistant)
The surface of the hard coat layer of the hard coat film with the pressure-sensitive adhesive layer was rubbed back and forth 50 times at a speed of 60 reciprocations / minute while applying a load of 2 kg / cm ² with steel wool (Bonstar # 2). The condition of the frictional portion was visually observed, and the scratch resistance was determined according to the following criteria.

  ◎: There was no scratch at the friction point.

  ○: One or two scratches were generated at the friction point.

  :: 3 to 5 scratches occurred at the friction point.

  X: There were six or more scratches in the friction portion.

  As apparent from Tables 1 to 3 above, the hard coat film of the present invention has very excellent scratch resistance. On the other hand, since the hard coat films of Comparative Examples 1 to 6 do not satisfy the constitution of the present invention, they were inferior in abrasion resistance.

Claims (12)

A hard coat film having a hard coat layer (a1) on at least one surface side of a substrate, wherein the hard coat layer (a1) has a double bond equivalent of less than 105 g / mol (a1-1) A compound (a1-2) containing 60% by mass to 95% by mass and a compound (a1-2) having a double bond equivalent of 105 g / mol or more and 200 g / mol or less, which is 100 g / mol or less Using a hard coat agent containing a compound (a1-1-1) having a heavy bond equivalent and a hydroxyl group-containing compound (a1-1-2) having a double bond equivalent of more than 100 g / mol and less than 105 g / mol Hard coat film characterized in that it is a layer formed. The hard coat film according to claim 1, wherein the hard coat layer (a1) has a thickness in the range of 3 μm to 25 μm. The hard coat film according to claim 1 or 2, wherein the compound (a1-1) is a compound having three or more (meth) acryloyl groups. The hard coat film according to any one of claims 1 to 3 , wherein the content of the compound (a1-2) contained in the hard coat layer (a1) is 5% by mass to 50% by mass. The hard coat film according to any one of claims 1 to 4 , wherein the compound (a1-2) is a compound (a1-2-1) having a (meth) acryloyl group and a urethane bond. The hard coat film according to claim 5 , wherein the compound (a1-2-1) is an aliphatic compound having two or more (meth) acryloyl groups and a urethane bond. The hard coat layer (a1) further claim 1-6 hard coating agent is a layer formed by using a containing the active energy ray-curable compound (Z) having a fluorine atom and a silicon atom 1 The hard coat film as described in a term. According to any one of claims 1-7 double bond equivalent of the entire active energy ray-curable composition is in the range of 95g / mol~130g / mol to be used for forming the hard coat layer (a1) Hard coat film. The hard coat film with an adhesive layer according to any one of claims 1 to 8 , further comprising an adhesive layer (a3). An information display device having a configuration in which the hard coat film according to any one of claims 1 to 9 is attached to at least one surface of a polarizing plate. The information display device according to claim 10 , wherein the thickness of the polarizing plate is in the range of 50 μm to 200 μm. On at least one surface of a polarizing plate, a portable electronic terminal having the configuration hardcoat film is stuck according to any one of claims 1 to 11.