TWI225159B - Hard coat film, substrate having the hard coat film laminated thereon and display device provided with same - Google Patents

Abstract

The present invention relates to a hard coat film that has excellent abrasion resistance and surface hardness, and improved curl and brittleness; a substrate having the hard coat film laminated thereon; and a display device provided with same. The hard coat film of the present invention is a hard coat film formed by laminating a hard coat layer on at least one side of a substrate film, wherein the product of the modulus of elasticity of the surface of the hard coat layer and the cube of the thickness of the hard coat layer is at least 30 KPa.mm<3> and at most 700 KPa.mm<3>. The hard coat film of the present invention preferably has a modulus of elasticity of the surface of the hard coat layer of least 4.0 GPa and at most 9.0 GPa, the hard coat layer is a layer formed mainly from a curable composition that can be cured by exposure to activation energy radiation, and the shrinkage in volume after curing of the curable composition is preferably 0% to 15%.

Description

1225159 V. Description of the invention (0) Technical field of the invention The present invention relates to a hard coating film with excellent abrasion resistance and surface hardness, and an anti-reflection layer, ultraviolet and infrared absorption layer, and selective wavelength absorption are provided on the hard coating film. Layer, an antistatic layer, an electromagnetic wave shielding layer, an anti-glare layer, and an antifouling layer, and a hard film with an organic film. Furthermore, the present invention relates to an image display device having a hard film Laminated film or its laminated substrate. In recent years, plastic products are replacing glass products from the viewpoint of processability and weight reduction. However, because the surface of plastic products is easily damaged, it is hard to adhere in many cases. The film is coated to provide scratch resistance. In addition, for conventional glass, in order to prevent scattering, the number of cases where a plastic film is bonded is increased. However, due to insufficient hardness of the film surface, a hard coating layer is widely formed on the surface. In the past, the production of hard coating films was generally formed by directly forming an active energy ray polymerizable resin such as a thermosetting resin or an ultraviolet curing resin. A thin coating film with a thickness of 3 to 15 μm is formed on an adhesive substrate film or through an intermediate layer of 1 μm or less. However, the hardness of the hard coating film on the hard coating layer is insufficient, and it is caused by the hardness of the coating film. With a thin thickness, the plastic substrate film on the bottom may be deformed, which may cause the corresponding hard coating layer to be deformed, and the hardness of the entire hard coating film may be reduced. Therefore, it cannot be fully satisfied. For example, it is widely used as Polyethylene terephthalate film of plastic substrate film 1225159 V. Description of the invention (3) The inclusion of the filler in the hard coating layer will make the layer thicker, and the hardness of the hard coating grease will be more improved, but the thicker it will be. The haze is increased, the hard coating layer is prone to crack or peel, and the curl of the hard coating film is increased due to hardening shrinkage. Therefore, it is difficult for the conventional technology to obtain a hard coating film with good characteristics in practice. Furthermore, Japanese Patent Application Laid-Open No. 2000-1 5 734 describes that a pencil hardness can be achieved by a hardened resin film layer having a specific elastic modulus, but it is difficult to achieve a pencil hardness of 5H or more. The first object of the present invention is to provide a hard coating film having a pencil hardness of 4H or more and a high surface hardness, improved curl or brittleness using a substrate film such as a PET film, and an organic film with an organic film. The hard coating film has functions such as anti-reflection, anti-glare, and antifouling. A second object of the present invention is to provide a base material on which the hard coating film is laminated. A third object of the present invention is to provide an image display device '' A substrate provided with a hard coating film or a laminated layer thereof. Means for solving the problem The following solutions have been found to achieve the above-mentioned first problem. A hard coating film is formed by laminating a hard film on at least one side of a substrate film. The formation of the coating layer is characterized in that the product of the surface elastic modulus of the hard coating layer and the cubic product of the thickness of the hard coating layer is 30 KPaMiim3 to 7 0 0 KP a · m m3 〇 In addition, the following solutions have been found to achieve the second Topic. 1225159 V. Description of the invention (4) A substrate laminated with the hard coating film. In addition, the following solution was found to achieve the third problem. In the present invention, a micro surface hardness tester (Fisher & Ins. Rumitz, Fisher's Tester H100VP-HCU) is used to determine the surface elastic modulus. Specifically, a square-shaped indenter made of diamond (opposite tip angle: 136 °) was used, and the indentation depth was not more than 1 μΐΉ. The indentation depth under an appropriate test load was measured. The load and displacement changes when the load was removed. Find the modulus of elasticity. Embodiments of the Invention Embodiments of the present invention will be described in detail below. The base film used in the hard coating film of the present invention is preferably a plastic film, such as polyester such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, triethyl cellulose, Cellulose resins such as cellulose acetate, polyolefins (polypropylene, polyethylene, polymethylpentene, syndiotactic polystyrene, and other polystyrene 'cyclic olefins such as phenolic lacquer-based resins (for example, Japan Leon) Leonjoya Co., Ltd., Ronenkus Co., Ltd., and Adon Co., Ltd., etc .; polymaple, polyether hydrazone, polyarylate, polyetheramide, polymethyl methacrylate, and polyether ketone, etc. The thickness of the film is preferably from 20 to 500 μm. If the thickness is too thin, the strength of the film becomes weak, and if the thickness is too large, the stiffness becomes too large, preferably from 80 to 200 μm. Here, 20 to 500 μm means "2〇 μηι or more and 500 μηι or less ". In the present invention, the following are the same. The substrate film is preferably transparent, and the light transmittance of the transparent substrate film is 80% or more in the wavelength range of 400nm ~ 780nm. Better than 90%

1225159 V. Description of the invention (5). A sheet-like or panel-like substrate other than a film is preferably a transparent substrate, and of course, it can also be applied to the hard coating layer of the present invention. In order to reduce the deformation of the base film, it is effective to increase the elastic modulus of the base film. On the other hand, if the deformation of the hard coating layer is small, the stress of the base film is reduced. As a result of the review, it is found that the hard coating layer is enlarged. The stiffness is effective. The rigidity of the hard coating is proportional to the amount of flexural rigidity related to the elastic modulus and film thickness. When the elastic modulus χ (the third power of the film thickness) related to the rigidity of the hard coating layer is within a specific range, the hardness of the pencil can be achieved because the rigidity becomes larger. If the bending rigidity of the hard coating layer is small, the hard coating layer itself is easily deformed, the load of the lead pen test is trapped in the base film, and the base film is deformed. If the bending rigidity of the hard coating layer is large, the deformation due to the load of the pencil test is small, and therefore the deformation of the base film can be suppressed. Although a large flexural rigidity is preferred, the substrate film must have a certain flexural strength or less for the handling of the roll. The cubic product of the surface elastic modulus of the hard coating layer and the thickness of the hard coating layer is preferably 30 KPa, mm3 to 700 KP a · m m3, particularly preferably 100 KP a · m m3 to 4 〇 0 KP a · m m3 〇 In order to prevent the damage caused by the pencil hardness test, the hardness of the hard coating layer itself is preferably to a certain degree, and the surface elastic modulus of the hard coating layer is 4.0 GPa or more, preferably 4.5 GPa or more. A hard coating layer having a surface elastic modulus lower than 4.0 GPa cannot obtain sufficient pencil hardness and scratch resistance. On the other hand, 'increasing the surface elastic modulus is effective to increase the hardness. 1225159 V. Description of the invention (6) However, the brittleness becomes worse, so the surface elastic modulus is preferably 9 · OGPa or less, and more preferably 7.0GPa or less. The surface elastic modulus of the hard coating layer is preferably 4.0 GPa to 9.0 GPa, and more preferably 4.5 GPa to 7.0 GPa. The surface elastic modulus of the hard coating layer can be adjusted by selecting a polyfunctional monomer or a polymer containing a polymerizable group by using a hardenable composition 'cured by heat or active energy rays to change the crosslinking density'. The hard coating layer may be adjusted by adding inorganic fine particles of metal oxides such as silica, alumina, and titanium dioxide, or organic fine particles such as a crosslinked polymer. The thickness of the hard coating layer of the present invention is preferably 10 μm or more, and more preferably 20 μm or more. Increasing the thickness can increase the hardness of the pencil, but the film will be difficult to bend 'and it will easily break when bent, so it is below 60 μιη', preferably 50 μm or less, more preferably 10 to 60 μm, particularly good 20 ~ 60μιη, optimally 20 ~ 50μηι. The hard coating layer is formed of at least one layer, and may be in the form of two or more layers. In the present invention, when the hard coating layer is rounded as the outer side, the smaller the crackability of the hard coating layer represented by the curl diameter when a crack occurs in the hard coating layer, the better. The crackability of the hard coating layer of the present invention is preferably 150 mm or less, and more preferably 80 mm or less. As the hard coating layer used in the present invention, a known hardening composition can be used. The curable composition is a thermosetting composition, an active energy ray polymerizable composition, and the like. Melamine 1225159 using a thermosetting composition can be used. V. Description of the invention (7) Crosslinking reaction of prepolymer such as resin, urethane resin, epoxy resin, etc., or sol-gel reaction of silicate However, from the viewpoint of ease of reaction control, it is preferable to use an active energy ray polymerizable resin. The hard coating layer in the present invention is preferably a layer mainly composed of a hardenable composition which is hardened by irradiation with active energy rays. In the present invention, "the hardening composition which is hardened by irradiation of active energy ray as a main body" means in addition to the hardening composition which is hardenable by active energy ray, and may contain inorganic or organic fine particles and a polymerization initiator described later. And other additives. The curable composition containing a compound containing an active energy ray-reactive polyfunctional polymerizable group or a crosslinkable group generally suffers from shrinkage in volume during curing, thickening of film thickness and large curl. In order to make the curl small, it is best to use a small shrinkage when hardened. The volume shrinkage before and after curing at 25 ° C is 0 to 15%, preferably 0 to 13%, and more preferably 0 to 11%. The volume shrinkage by hardening can be determined from the density change of the hardenable composition before and after hardening. Specifically, the density (25 ° C) measured by MULTIVOLUME PYC NOMETER manufactured by Microtron Corporation was used to obtain the density from Mathematical Formula A: Mathematical Formula A: Volume shrinkage ratio = {1- ( Density before hardening / Density after hardening) χ100 (%) By reducing the volume shrinkage rate of the hard coating layer when it is hardened, the curl of the hard coating film formed by laminating the hard coating layer on the base film may be small. Practically, at 25 ° C and 60% RH, the curl of the hard coating film is 1225159 V. Description of the invention (8) is in the range of -15 to +15. In addition, the curling 値 is smaller than the thickness of the hard coating, that is, the curling 値 divided by the thickness (μιη) of the hard coating (absolute 値) is preferably as small as possible, and it is preferably 0.45 (1 / πι · μηι) or less, especially 0.35 (1 / ηι · μηι) or less. Here, the curling 値 is a 値 obtained by the following mathematical formula B. Mathematical formula B: curl 値 = 1 / R (R is the radius of curvature (m) of the curl), and the hard coating layer expands and contracts due to the amount of moisture absorption. The absolute value of the difference between the curling temperature at 25 ° C0% RH and 25t: 80% RH is preferably 24 or less. In order to suppress the modification of the curling ，, the hydrophilicity of the hardened composition after hardening by active energy ray irradiation is preferably small, and the I / O 値 of the hardening composition after curing related to hydrophilicity is preferably 0.1 to 0.85. , More preferably 0.25 to 0.8, and most preferably 0.35 to 0.75. If I / O 値 exceeds 0 · 8 7 5, the hydrophilicity of the polymer produced by hardening becomes high, the volume expansion or hardness of the hard coating layer is greatly affected by humidity, and it has high surface hardness and it is difficult to obtain Hard coating film with good curl characteristics. If the I / O ratio is too small, the hygroscopic expansion is small and the curl at room temperature is large. The above I / O 値 are based on "Pure System of Organic Qualitative Analysis by Fujita Mu" (Fukama Bookstore, published in 1970), and "Organic Mind Map" by Koda Shansheng (published by Sankyo, issued in 1984) "Inorganicity (I) / Organicity (〇)" obtained by the method described in. I / O 値 is a means for predicting various physical and chemical properties of organic compounds. Organic properties are obtained by comparing the number of carbons, and inorganic properties are obtained by comparing the boiling points of hydrocarbons of the same number of carbons. For example, (-CH2-) (actual-1 0-1225159 V. Description of the invention (9) is C) The organic nature of one is set to 20, and the inorganicity is caused by the effect of the hydroxyl group (-0H) on the boiling point, so The inorganic property was defined as i 00. Based on the inorganic fluorene of (-OH) as a reference, the fluorene of other substituents (inorganic groups) was obtained, and the "inorganic radical table" was prepared. The hardening composition for forming the hard coating layer is hardened by irradiation with active energy rays, and the above ratio of inorganic 値 to organic 値 is used as I / O 値. That is, the I / O ratio of the hardenable composition hardened by the active energy ray irradiation is the total of the I / O ratio per repeating unit of the polymer produced by the active energy ray irradiation multiplied by the mass fraction of each repeat unit. value. By appropriately setting the composition of the hardenable composition before hardening, the I / O ratio of the hardenable composition hardened by irradiation with active energy rays can be 0.1 to 0.85. For example, by reducing the -OH, -COOR, -NH2, -CO- and other groups in the hardened composition, I / O 値 can be controlled to 0.1 to 0.85. Furthermore, by suppressing the I / O 値 of the curable composition within the above range, the amount of moisture absorption can be reduced. The moisture absorption of the hard coating layer of the present invention at 25 ° C 60% RH is preferably 3% by mass or less, more preferably 2.5% by mass or less, compared with the hard coating layer when dried. It is 2% by mass or less. The formation of the active energy ray polymerizable resin layer which is preferably used as the hard coating layer of the present invention can be formed from an oligomer containing a polyfunctional monomer and / or a polymerizable functional group or a crosslinkable reactive group in a side chain. , A coating solution of a polymer and a polymerization initiator is formed by coating a polyfunctional monomer, an oligomer, and a polymer on the above-mentioned base film. The -11 · 1225159 V. Description of the invention (10) The polymerizable functional group of the active energy ray polymerizable resin layer is preferably a radical polymerizable unsaturated double bond group or a ring-opening polymerizable cyclic ether group. The polymerizable unsaturated double bond group may be, for example, acrylfluorenyl, methacrylfluorenyl, vinyl, allyl, or the like. From the viewpoint of reactivity, acrylfluorenyl and methacrylfluorenyl are more preferably used. Specific examples of the monomer having a polyfunctional polymerizable unsaturated double bond group are diol-based (meth) acrylic acid such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate. Esters, n-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tri (meth) acrylate, di-trimethyl tetra (meth) acrylate Methylolpropane ester, isopentaerythritol tri (meth) acrylate, isopentaerythritol tetra (meth) acrylate, diisopentaerythritol penta (meth) acrylate, hexa (meth) acrylate di Isopentaerythritol ester, 1,4-cyclohexanediol di (meth) acrylate, 1,3,5-cyclohexanetriol tri (meth) acrylate, adipic acid, sebacic acid, phthalic acid , Isophthalic acid, terephthalic acid, and diols (such as ethylene glycol, polyethylene glycol, propylene glycol, etc.), or triols (glycerol, trimethylolpropane, etc.) are polyester polyols Polyol polyacrylates such as reactants of oligomers and (meth) acrylates, bisphenol A and glycidyl (meth) acrylate, Polyisocyanate polyurethane oligomers formed from the reaction products of hexanediol and glycidyl (meth) acrylate, such as acrylate epoxy esters, condensation products of polyisocyanates and polyols, and (methyl ) Reaction of hydroxyl-containing acrylates such as hydroxyethyl acrylate, etc. to obtain urethane acrylates and the like. -12- 1225159 V. Description of the invention (11) In addition, the ring-opening polymerizable cyclic ether compound is, for example, a cyclic suboxide such as an epoxy derivative, an oxetane derivative, a tetrahydrofuran derivative, or an oxazoline derivative. Amine ethers and the like are preferably epoxy derivatives, oxetane derivatives, and oxazoline derivatives. These ring-opening polymerizable ether compounds preferably have two or more ring structures in the same molecule, and more preferably three or more ring structures as described above. For example, the trifunctional glycidyl ether may be trimethylolethane triglycidyl ether, trimethylol glycidyl glycidyl ether, glycerol triglycidyl ether, triglycidyl hydroxyethyl isotricyanic acid For example, esters, tri- or higher-functional glycidyl ethers are, for example, sorbitol tetraglycidyl ether, isopentaerythritol tetraglycidyl ether, polyglycidyl ether of cresol novolak resin, polyglycidyl phenol novolac resin Glycidyl ether and the like, epoxy resins having trifunctional or higher functions can be, for example, epoxide GT-301, epoxide GT-401, EHPE (above, manufactured by Daisier Chemical Industry Co., Ltd.), phenol novolac resin Examples of polycyclohexyl methyl ether and the like include trioxane or higher azacyclobutanes such as OX-SQ and PNOX-1009 (above, manufactured by Toa Sangyo Co., Ltd.). In order to adjust the surface elastic modulus, reduce the hardening shrinkage, and improve the adhesiveness, a monofunctional monomer may be added to the polyfunctional monomer as appropriate. The monofunctional monomer may be, for example, alkyl (meth) acrylate, alkyl (meth) acrylate, and the like, hydroxyethyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate. Polar group-containing acrylates such as glycidyl (meth) acrylate, (meth) acrylamide, N-13-1225159 5. Description of the invention (12) Hydroxymethyl (meth) acrylamide Acrylamide, an existing monomer such as N-vinylpyrrolidone, styrene, vinyl acetate, and maleic anhydride. On the other hand, a compound having one or two ring-opening polymerizable groups in the same molecule may be used as appropriate. The preferred compounds are monofunctional or bifunctional glycidyl ethers, monofunctional or bifunctional alicyclics. As the epoxy, monofunctional, or bifunctional azetidine, various commercially available or known compounds can be used. Similarly, an oligomer or polymer containing at least two or more radically polymerizable groups may be added to the polyfunctional monomer. The oligomer or polymer containing a radical polymerizable group may be, for example, an oligomer or polymer having a polymerizable group such as a (meth) acrylfluorenyl group or an allyl group in a side group. Hydroxyl oligomers, polymers and ester derivatives of (meth) acrylic acid, oligomers and polymers with carboxylic acids, and hydroxyl-containing (meth) acrylates (hydroxyethyl methacrylate), etc.) Dehydrochlorination reaction of synthetic ester derivatives such as allyl alcohol, epoxy ring-opening polymer oligomers and polymers such as glycidyl (meth) acrylate, oligomers and polymers with chloroethyl groups Synthesized acrylic polymer and the like. Further, as the compound having three or more ring-opening polymerizable groups in the same molecule, a crosslinkable polymer containing a repeating unit represented by formula (1) is particularly preferred. R1 in formula (1) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group. L1 is a single bond or a divalent link -14-1225159 V. Description of the invention (13), preferably a single bond, -0-, alkylene, aryl, and * -C00 linked to the main chain on the * side -, 氺 -C0NH-, 氺 -0C0-, 氺 -NHC0-. p1 is a monovalent group containing a ring-opening polymerizable group, and P1 is preferably an imine ether ring containing an epoxy ring, an azetidine ring, a tetrahydrofuran ring, a lactone ring, a carbonate ring, an oxazoline ring, and the like. Etc. Among them, monovalent groups containing an epoxy ring, an azetidine ring, and an oxazoline ring are particularly preferred. The crosslinking monomer of the present invention containing a repeating unit represented by the formula (1) is preferably synthesized by polymerization of a corresponding monomer because it is relatively simple. In this case, radical polymerization is the simplest polymerization reaction and is therefore preferred. Specific examples are polyglycidyl methacrylate, polyglycidyl methacrylate, polycyclohexyl methyl methacrylate, poly-3-ethyl-3-azacyclobutyl methyl methyl Acrylate, etc. [Chem. 1] f-(&quot; CH2_C — ^-where R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, P1 is a monovalent group containing a ring-opening polymerizable group, and L1 is a single bond or two Preferred specific examples of the repeating unit represented by the formula (1) of the valence linking group are shown below, but the crosslinkable polymer system that can be used in the present invention is not limited to these specific examples. Invention description (14 CH3 (E-2) ch3

-ch2-c-J -ch2-c- ch3 cooch2ch-ck 〇 2 COOCH2CH2C-CH2 〇 (E-3) (E-4)

-CH2—CH I c〇och2ch——ch2 -ch2—? Hi— ch3 COOCH2CH2CsCH, 〇〇 (E-5) CH3 ch2 ~ c— (E-6) I / / GH2CH3 CO〇CH2p, rw / ch2 -CH2 --CH-) / CH2CH3 COOCH2C- ^ ch h2c, (E-7) CH〇I, ch2—c— (E-8) J2, -CH2—CH_

COOCH2CH CH.I L CH〇 CH: 〇

COOCH2CH CH CH2 CH h2 i &gt; (E-9) CH3 (E-1〇) -CH2—C- -ch2—ch- C00CH2CH2C00CH2CH-ch2 〇COOCH2CH2COOCH2CH-ch2 o -16- 1225159 V. Description of the invention (15 (E- 12) ch3 I CH2—c— CONHCH 2CH2OCH2〇H-CH2

〇 (B13)

-CH2—CH

(E-14) -f-CH2-CH-CH2OCH2CH-CH2.

cooch2ch—ch2 O (E-15) ch3 ch2—c— COOCH2CHCH2〇CH2CH—ch2

OH o

(E-17)

(E-20) Yaya 3 ch2—c— conhch2ch2och2ch ch, CH ^ h2 -17- 1225159 V. Description of the invention (16 (E-21) -f-CH〇-CH ~)-CH〇CHq COOCH2C, h2c, (E-23) CH, I, CHo—C— (E-22)

CHoCH, CONHCH2CH2〇CH2C, CH,

(E-26) (E-25) CH, -CH〇-C-, / CH3 COOCHoC——CH2 \ / 〇-ch2-ch-} — 〇η3 co〇ch2c-ch2 A monomer or oligomer having a saturated double bond group, a polymer, and a compound having a polyfunctional cyclic structure may be used in combination. When a monofunctional monomer, an oligomer or polymer containing at least two polymerizable unsaturated double bond groups, or a ring-opening polymerizable cyclic ether compound is added, the polyfunctional polymerizable unsaturated The amount of the double bond monomer is preferably 50% by mass or less, and more preferably 35% by mass or less. If monofunctional monomer, containing at least two or more polymerization-18-1225159 V. Description of the invention (彳 7) The proportion of oligomer or polymer of unsaturated unsaturated double bond group or ring-opening polymerizable cyclic ether compound is too large , The desired hardness cannot be obtained. By adding inorganic or organic fine particles to their active energy ray polymerizable resin layers to adjust the surface elastic modulus of the hard coating layer, the hardening shrinkage rate is small, and the curling of the hard coating film can be reduced. The microparticles may be, for example, inorganic oxides or internally crosslinked polymer resin particles. The inorganic oxide particles are preferably those having a high hardness, and the inorganic oxide particles having a Moss hardness of 6 or more are preferred. Examples include silicon dioxide particles, titanium dioxide particles, oxide pins, alumina particles, and the like. The organic fine particles may be, for example, resin particles of acrylic resin, polystyrene, polysiloxane, melamine resin, benzoin amine resin, polytetrafluoroethylene, cellulose acetate, polycarbonate, and nylon. Particle systems formed from polymethyl methacrylate (divinylbenzene copolymer), polysiloxane, polystyrene, melamine resin, benzoic acid amine resin, or a composite thereof are preferred. Furthermore, resin microparticles of a monomer having a bifunctional or more polymerizable group and a polymer which is internally crosslinked by copolymerization are preferred. The volume average particle diameter of these fine particles is 1 nm to 400 nm, preferably 5 nm to 200 nm, and more preferably 10 nm to 100 nm. Below lnm makes it difficult to disperse and may agglomerate particles. Above 400nm, the haze becomes larger. In both cases, the transparency is reduced, which is not suitable. The added amount of these fine particles preferably accounts for 5 to 80% by mass, more preferably 10 to 50% by mass, of the total amount of the lipid layer. In general, 'inorganic microparticles have poor affinity with active energy ray polymerizable resins, and therefore, it is easy to break the interface only by mixing the two with the system, and it is difficult to improve the scratch resistance. In order to improve the affinity of the inorganic microparticle active energy ray polymerizable resin, the inorganic microparticles may be treated with a surface modifier containing an organic segment. The surface modifier is preferably one which forms a bond with the inorganic particles and has a high affinity for the active energy ray polymerizable resin of the inorganic fine particles on the other hand. The compound that forms a bond with the surface of the inorganic fine particles is preferably a metal alkoxide such as silicon, aluminum, titanium, zirconium, or an anionic compound having a phosphate, phosphonic acid group, sulfate, sulfonate, or carboxylic acid ester. . In addition, the active energy ray polymerizable resin is preferably one having a chemical bond and an ethylene polymerizable group introduced at the end. For example, when an active energy ray polymerizable resin is synthesized from a monomer having an ethylenically unsaturated group as a polymerizable group and a crosslinkable group, the end of the metal alkoxide or anionic compound has a polymerizable unsaturated double bond group or Ring-opening polymerizable cyclic ether groups are preferred. In the present invention, when a plastic film is used as the base film, since the plastic film itself has low heat resistance, the hardening resin is hardened at a low temperature as much as possible when the hardening resin is heated. The heating temperature in this case is 140 ° C or lower, preferably 100 ° C. On the other hand, most of the hardening caused by the effect of light undergoes a cross-linking reaction at a low temperature, so it is a better user. -20- 1225159 V. Description of the invention (19) In the case where an active energy ray polymerizable resin is used in the hard coating layer, the active energy rays may be, for example, radiation, γ-rays, α-rays, electron rays, ultraviolet rays, and the like, and ultraviolet rays A method in which a polymerization initiator which generates radicals or cations by ultraviolet rays is added and hardened by ultraviolet rays is particularly preferred. Further, after ultraviolet rays are irradiated, they can be hardened by heating. The preferred heating temperature in this case is below 1 40 ° C. Examples of the photo-radical initiator include acetophenones, diphenyl ketones, michler's ketones, benzyl benzyl esters, benzoin, α-methoxyl esters, tetramethylamine sulfanil, and thiophene Tons of ketones and so on. In addition to the photopolymerization initiator, a photosensitizer may be used. Examples of the photosensitizer include n-butylamine, triethylamine, triethanolamine, tri-n-butylphosphine, thioxanthone, and the like. The cationic photoacid generator can be a compound such as a triarylsulfonium salt, a diaryl iron iodide salt, or a nitrobenzyl ester of a sulfonic acid. The Organic Electronic Materials Research Institute may compile "Organic Materials for Imaging". The compounds described in the journal (1 997) and the like and various known photoacid generators. Among them, sulfonium salts such as diphenyl-4-thiophenoxyphenyl hexafluoroacetonium antimony or diphenyliodonium phosphonium salts are preferred, and the paired ions are preferably PF6_, SbF6_, AsF6-, B (C6F5) 4- etc. A monomer or oligomer containing a polyfunctional polymerizable unsaturated double bond group, a polymer, a polyfunctional ring-opening polymerizable cyclic ether compound, a radical photoinitiator, and a cationic photoacid can be mixed and used. As the generator, -21-1225159 which can generate both free radicals and cations can be used alone. 5. Description of the invention (20) Compound. The amount of the polymerization initiator is 0.1 to 15 parts by mass, and preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional monomer. By dissolving the above-mentioned polyfunctional monomer and polymerization initiator in an organic solvent such as ketones such as methyl ethyl ketone, methyl isobutyl ketone, alcohols such as ethylene glycol, isopropanol, and esters such as ethyl acetate A coating solution of an active energy ray polymerizable resin is prepared in a system or the like. In order to omit the drying step, there may be no solvent. Active energy rays can be obtained by known thin film forming methods such as immersion method, spin coating method, spraying method, roll coating method, gravure printing method, smearing method, extrusion method, plating method, die coating method, etc. The polymerizable resin is formed on a base film, and then dried and irradiated with active energy rays to produce a hard coating film of the present invention. Furthermore, in order to provide an adhesive for the base film and the hard coating layer, a surface treatment such as an oxidation method or an unevenness method may be applied to one or both surfaces as necessary. The oxidation method is, for example, corona discharge, glow discharge, plasma treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. Further, more than one undercoat layer may be provided. The raw material of the undercoat layer may be, for example, a copolymer of vinyl chloride, vinylidene chloride, butadiene, (meth) acrylate, vinyl ester, or the like, a water-soluble polymer such as plastic, a low molecular weight polyester, or gelatin. A metal oxide such as tin oxide, ITO, or lead oxide or an ionic organic compound may be added to the undercoat layer as a conductive material. -22- 1225159 V. Description of the invention (21) The hard coating can be a single layer or composed of two or more layers. Layers having different surface elastic moduli can be laminated in order to form a multilayer structure. In the case of a multilayer structure, the elastic modulus, hardening shrinkage, I / O 値, and moisture absorption of the layer can be calculated from the characteristics of each layer by the thickness. The hard coating layer of the present invention may be provided with a functional film such as an antireflection layer, an antiglare layer, and an antifouling layer. Furthermore, an ultraviolet or infrared absorbing layer, a wavelength absorbing layer, an antistatic layer, and an electromagnetic wave shielding layer can be laminated in combination to provide a hard coating film with a high-hardness functional film. The functional film can be formed by applying a known functional material by a wet method, a dry method such as sputtering, or a vacuum deposition method such as vapor deposition. Fig. 1 is an embodiment of the present invention and shows the layer structure of a hard coating film. Fig. 2 is another embodiment of the present invention, showing a layer structure of a hard coating film with an organic thin film. In Figures 1 and 2, 1 is a base film, 2 is a hard coating layer, 3a is a high refractive index layer, 3b is a low refractive index layer, and 4 is an antistatic undercoat layer. The substrates laminated with these hard coating films can be suitably used as substrates having excellent scratch resistance and surface hardness. Specifically, the base material may be, for example, a hard-coated plastic sheet to prevent surface damage, or a hard-coated window or window glass to prevent scattering. The hard coating film can be laminated with an adhesive and attached to a substrate. The hard coating film is preferably attached to only one side of the substrate, but may be attached to both sides of the substrate. 23-1225159 V. Description of the invention (22). For example, glass or plastic can be used as the substrate of the hard coating. Specific examples of plastics may be cellulose esters, polyamides, polycarbonates, polyesters, polystyrenes, polyolefins, polymills, polyether maples, polyarylates, polyetherimines, polymethacrylates Esters and polyetherketones. The substrate is preferably transparent, and the wavelength of light transmission of the substrate from 400 nm to 780 nm is 80% or more, preferably 90% or more. The thickness of the base material is preferably 1 to 30 mm, and the base material may be any of a sheet shape, a flat plate shape, and a plate shape. The image display device provided with the hard coating film of the present invention or the substrate on which it is laminated is preferably used as an image display device having excellent scratch resistance and surface hardness. An image display device provided with a hard coating film or a laminated base material such as a liquid crystal display (LCD), a plasma display panel (PDP), an electric field emission display (FED), or an electroluminescence display (ELD). FPE (flat panel display) or cathode tube display (CRT), touch panel, etc. Fig. 3 is a sectional view showing an image display device provided with a hard coating film according to still another embodiment of the present invention. Fig. 4 is a sectional view showing an image display device of a substrate provided with a hard coating film, which is another embodiment of the present invention. In FIGS. 3 and 4, A is an image display device, B is a substrate, and C is a hard coating film or a hard coating film with an organic thin film. The following examples are used to illustrate the present invention, but the present invention is not limited by it. -24-1225159 V. Description of Invention (23). (Production of hard coating film) The curable resin described in Table 1 was dissolved in methyl ethyl ketone (MEK), a polymerization initiator was added, and the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a curable composition. Corona treatment in advance, mixed with a mass ratio of 5: 5, a copolymer made of styrene butadiene copolymer (LX407C5; manufactured by Nihon Leon Co., Ltd.) with a glass transition temperature of 37 ° C, and tin oxide · oxidation Antimony composite oxide (FS-10D; manufactured by Ishihara Sangyo Co., Ltd.), coated with a film thickness of 0.25 μm after drying to form an antistatic undercoating film with a thickness of 175 μm (biaxially stretched terephthalic acid) Acid ethylene glycol film) and another 80 μηι triethyl cellulose cellulose film. A hardening composition of a desired thickness is applied to the two films to which the antistatic property is applied by extrusion (the thickness is adjusted by the dissolving concentration and the coating amount of the hardening composition). After drying the hardenable composition at 100 ° C, it was irradiated with ultraviolet light at 750 mJ / m2 to form a hard coating layer, and a hard coating film was prepared (the sample with t is coated on triethyl cellulose) ). In the case of a radically polymerizable hardening composition, the initiator is Iruka Guinea 184 (produced by Ciba Gage Corporation), and in the case of a cationically polymerizable composition, the initiator is Ruodexilu 2074 (Ruode (Manufactured by Yasuji), when the two are mixed, a mixture of these initiators is used. The added amount is 4% by mass based on the curable resin. Polyglycidyl acrylate in the table * refers to methacrylic acid 25-1225159 V. Description of the invention (24) Glycidyl acid is dissolved in MEK, and the reaction is performed at 80 ° C for 2 hours while dropping the initiator. The obtained reaction solution was dropped into hexane, and the precipitate was dried under reduced pressure to obtain the obtained product. In addition, the molecular weight is 15,000, and the alumina dispersion ** is obtained by mixing 234 parts of methyl isobutyl ketone and 36 parts of Aronicus M-5300 (carboxylic acid group-containing methacrylate; East Asia Synthesis). Co., Ltd.), 180 parts of a mixture of fine particles of alumina (AKP_G015; Sumitomo Chemical Industry Co., Ltd.), the surface is treated with a ceramic-coated sand mill using oxidized pin beads as a medium and dispersed. Dispersion of alumina particles. The mass in the table is the mass of the solid content. (Characteristics of Hard Coating Film) Table 1 shows the product of the surface elastic modulus and the cubic power of the thickness, the surface elastic modulus, the thickness, and the hardening shrinkage of the hardened composition of each hard coating film produced. , PET, or triethyl cellulose, as the substrate film, pencil hardness, curling, cracking, etc. of the hard coating. -26- 1225159 V. Description of the invention (26) 19 The present invention 529 5Η 5.8 45 5 or less u 40 20 Comparative Example 6 Diisopentyl tetraacrylate (manufactured by Benwa Pharmaceutical Co., Ltd.) / Alumina dispersion 0 mixture (75/25 quality ratio) 15 3Η 8.9 12 5 or less 80 100 21 Comparative example 139 4Η 8.9 25 15 15 100 150 22 Comparative example 382 5Η 8.9 35 20 130 200 to i 23 Comparative example 811 5Η 8.9 45 25 “200 to J; 24 Comparative example UV6300 (urethane acrylate; manufactured by Japan Synthetic Chemical Industry Co., Ltd.) 10 2Η 4.6 13 12 5 or less 200 g 40 25 Comparative Example 181 4Η 4.6 34 8 300 g or more 50 26 Comparative Example 366 4Η 4.6 43 10 "50 27 Comparative example 575 5Η 4.6 50 15" 100 28 Comparative example Piscat # 230 (Diacrylic acid hexamethylene distillate. 士 βίά Right fiber 14 2Η 4.2 15 18 5 or less 150β 50 29 Comparative example 66 4Η 4.2 25 10 200g 100 30 Comparative example On the 13th, August 8th, Co., Ltd. Chemical Industry Co., Ltd. 180 4 35 4.2 35 25 "120 31 Comparative Example 383 4Η 4.2 45 30 250g 150 32 Comparative Example ΕΡΑ 3150 (epoxy side alicyclic ring Oxygen resin; manufactured by Daisier Chemical Industry Co., Ltd.) 27 2Η 3.4 20 2 5]; 100 g 30 or less 33 Comparative Example 218 4 Η 3.4 40 5 or less 120 g 30 or less 34 Comparative Example 425 4 Η 3.4 50 5 or less 150 g 30 or less 35 Comparative Example Diisopentaerythritol hexaacrylate Co., Ltd.) / alumina dispersion ** mixed (70/30 mass ratio) 10 3Η 9.8 10 10 5 11 50 g or less 150 36 Comparative Example 78 4Η 9.8 20 10 “200 to i 37 Comparative Example 420 5Η 9.8 35 15 "200 to i 38 Comparative Example 893 6Η 9.8 45 20" 200 to J: -28-1225159 V. Description of the invention (27) Sample hardened resin surface elastic mold pencil surface elastic film thickness hardened curled 値 sharp pen scratch crack Number of properties X Thickness 3 Hardness ratio shrinkage ratio (mixed mass ratio) KPa * mni3 GPa μηι vol% 1 / ιη mm It Comparative Example 7 Η 6.8 10 5 2,000 g_ 30 or less 2t Comparative Example 6 Acrylic acid diisocyanate Pentaerythritol ester (manufactured by Nippon Kayaku Co., Ltd.) 484 4Η 6.8 30 21 20 300 g or more 80 3t Comparative Example 662 4Η 6.8 46 30 “120 4t Comparative Example 850 4Η 6.8 50 45“ 150 13t Comparative Example 1290K (Propanic acid Amines 23 Η 6.8 15 5 or less 250g 30 or less 14t ratio Comparative Example Ester; Dessier Chemical Industry Co., Ltd. 244 4Η 6.8 33 10 5 or less 300g or more and 30 or less 15t Comparative Example 579 4Η 6.8 44 10 "30 or less 16t Comparative Example 850 4Η 6.8 50 15" 30 or less

As can be seen from Table 1, the cubic product of the surface elastic modulus of the hard coating layer and the thickness of the hard coating layer is 30 KPa * mm3 to 700KPa * mm3, and a hard coating film having a pencil hardness of 4H or more can be obtained.

Still more preferably, by using a hard coating material having a volume shrinkage ratio of 15% or less after hardening, a hard coating film having a small curl can be obtained. When the surface elastic modulus of the hard coating layer is 9 GPa or more, the hardening shrinkage is small and the brittleness is significantly deteriorated, and the hard coating layer is also broken. In addition, Table 2 shows the cubic product of the surface elastic modulus and thickness of the produced hard coating layer, the surface elastic modulus, the thickness, the curing shrinkage of the cured composition, and PET or triethyl cellulose as the base film. The pencil hardness, curling, and breakability of the hard coating at the time. -29- 1225159 V. Description of the invention (28) Table 2 Sample No. Hardenable resin surface elastic modulus X thickness 3 Pencil hardness Surface elasticity film thickness Hardening shrinkage rate Curl I / O Curl humidity difference Moisture absorption rupture ( Mixing mass ratio) KPa * mm3 GPa μηι vol% 1 / ιη 丨 80% ~ 10% 丨 mass% mm 3 Palladium hexaacrylate diisopentaerythritol (manufactured by Japan Chemical Company) 662 5H 6.8 46 21 33 28 0.93 3.5 140 7 mm isopentaerythritol tetraacrylate (manufactured by Japan Chemical Co., Ltd.) 565 5H 6.2 45 20 25 26 0.86 3.2 120 11 Trimethylmethanepropane triacrylate (Nippon Kayaku Co., Ltd.) )) 547 5H 6.0 45 19 30 19 0.72 2.5 120 19 mm trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd.) / glycidyl polymethacrylate * · mixture (75/25 mass ratio) 529 5H 5.8 45 13 5 or less 18 0.71 2.2 40 40 Woofing triacrylate trimethylolpropane vinegar (manufactured by Nippon Kayaku Co., Ltd.) / Polyglycidyl methacrylate * mixture (50/50 mass ratio) 492 4H 5.4 45 11 5 or less 17 0.69 2.0 30 or less 41 glycosyltriacrylate trimethylolpropane (Manufactured by Nippon Kayaku Co., Ltd.) / Polyglycidyl methacrylate * mixture (25/75) 487 4H 5.0 46 8 5 or less 14 0.68 1.9 30 or less 42 isopentaerythritol hexaacrylate Co., Ltd.) / Xiruoji Seide 2021P (epoxy resin; Daicil Chemical Co., Ltd.) (75/25) 467 4H 4.8 46 10 5 or less 18 0.66 1.8 30 or less 43 Isoprene hexaacrylic acid of the present invention Alcohol ester (manufactured by Benhwa Pharmaceutical Co., Ltd.) / EHPA3150 (now oxygen side alicyclic epoxy resin; manufactured by Thiexil Chemical Industry Co., Ltd.) (70/30) 501 5H 5.5 45 13 5 or less 20 0.79 2.6 40 -30- 1225159 V. Description of the invention (29) From the results in Table 2, it can be seen that when the product of the surface elastic modulus and the cubic power of the thickness is large, the hardening shrinkage of the hardened composition is less than 15%, and the I / O 値 is 0.85. In the following, the goals of reducing pencil hardness, curl, breakability, and moisture absorption can be achieved, and the expansion and contraction of the hard coating layer due to moisture absorption can be reduced. (Formation of anti-pollution anti-reflection layer) (1) Preparation of high refractive index layer coating liquid (a-1) Disperse 30.0 parts by mass of titanium dioxide particles by a sand mill (TTO-55B, manufactured by Ishihara Industry Co., Ltd.) , 4.5 parts by mass of an anionic monomer (M-5300, manufactured by Toa Kosei Co., Ltd.) and 65.2 parts by mass of cyclohexanone, to prepare a titanium dioxide dispersion having a mass average diameter of 55 nm. The above-mentioned titanium dioxide dispersion, diisopentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Ilukage 907, manufactured by Ciba Gage Corporation), and a photosensitizer (Kayakiya DETX, manufactured by Nippon Kayaku Co., Ltd.) The total volume of monomers (the total amount of diisopentaerythritol hexaacrylate and anionic monomers) and the volume ratio of titanium dioxide is 60/40. The mass ratio of the photopolymerization initiator to the photosensitizer is 3/1, so the mass ratio of the total amount of the photopolymerization initiator to the photosensitizer and the total amount of the monomer becomes 6/100. Methyl ethyl ketone is added and mixed to adjust High refractive index layer coating solution. The refractive index is 1.80. (2) Preparation of low-refractive index layer coating solution (a-2): 6 g of isopentaerythritol tetraacrylate (PETA, manufactured by Nippon Kayaku Co., Ltd.) and 0.5 g of photopolymerization initiator (Ilu Cajia 184, Ciba Geigy-31-1225159, and I will make it clear that (31) PET film 47 layer only PET film 6% 〇X 1 back and forth 3 From Table 3, it can be seen 'by the hard coating in the present invention A laminated antifouling antireflection layer on the film can obtain a hard coating with an organic thin film that has both antifouling and antireflection functions. (4) A hard coating with an antifouling antireflection layer The film image display device was coated with an acrylic adhesive on the surface of the film of Example 44 or 46 without a hard coating layer or an antifouling anti-reflection layer, and it was bonded to PDP: 42 type plasma display manufactured by Hitachi, Ltd. (CMP4121HDJ) The glass surface of the front panel (a panel with a conductive layer, a selective absorption filter layer, and a near-infrared absorption layer) and the plastic surface of the video display part of Nintendo Co., Ltd.'s handheld upstream game instrument Gameboy. Ease, dirt ease, scratch resistance, etc. The results are shown in Table 4. Table 4 Samples Fingerprint erasability on a film screen of a display device, scratch-off, stylus, scratch-resistance, numbering, ease of viewing 48 PDP panel 44 〇300 g over 60 times back 49 ”46 〇050 g under 5 times back 50” Arr Ws X Δ 3〇 〇gram above 100 rounds and over 51 Gameboy 44 〇〇〇３００〇 over 60 rounds 52 "46 〇〇〇50 grams below 5 rounds 53" / firrr ΓΠ1Γ j \\\ X Δ Below 50 grams 1 round-33- 1225159 V. Description of the invention (32) As can be seen from Table 4, the surface hardness of the image display device provided with the hard coating film of the present invention is large, so it is difficult to damage, and the image is excellent in visibility. Each evaluation method is performed according to the following methods. Surface elasticity Modulus: A micro surface hardness tester (Fisher & Inslum) (Fisher H100VP-HCU) is used, and a diamond-made square-shaped indenter (point opposite angle: 136 °) is used for measurement. The indentation depth under load is determined by the change in load and displacement when the load is removed. The hardening shrinkage of the hardened composition: In accordance with the method already described. Pencil hardness test: pencil scratch The hardness of the scratch test was performed under the conditions of temperature 25 ° C and relative humidity 60%, and the hard coating film was adjusted for 5 hours, and then tested with a test pencil specified in JIS S6006. Pencils specified in JIS K5 400 In the hardness evaluation method, no scratches or dents are found under the load of 9.8 N. The sharpness of a pencil is sharp. Scribes: The film is conditioned for 5 hours at a temperature of 25 ° C and a relative humidity of 60%. In the HEIDON surface property testing machine N-14 (made by Shinto Science Co., Ltd.), the load and side friction of the metal tip of a stylus tip (PE355, manufactured by Pentel Co., Ltd.) tilted at 45 ° C were investigated, and investigation occurred. Load when damaged. Curl curl: The curl measured by the template for curl measurement of method A of "A curl measurement method for photographic film" of JIS K76 1 9-1 988. The test conditions for 60% curl are 25 ° C and 60% relative humidity. Ben-34- 1225159 V. Explanation of the invention (33) When the curl is positive in the invention, it means that the hard coating side of the film becomes the curl on the inside of the coating, and when it is negative, it means that the coating side is on the outside of the curvature. curly. The larger the salamander, the more obvious the curl. Curl humidity difference: Read the curl 値 at 25 ° C relative humidity 80% and 10%, expressed as the absolute 値 difference between the two curl 値. Breakability: The hard coating film with a width of 35 mm was left in an environment of 25 ° C and 60% RH for 5 hours, then the hard coating layer was rounded as an outer side, and the curl diameter was obtained when the hard coating layer was cracked. I / O 値 of hardened composition: According to the method already described. Moisture absorption: After drying in a dry atmosphere at a dew point of -40 ° C for 2 hours, it is then placed in 25% 60% RH for 3 hours. The moisture absorption is determined from the weight change before and after the storage. Surface reflectance: A spectrophotometer (manufactured by JASCO Corporation) was used to determine the surface reflectance of regular reflection when the incident light was 5 ° in a wavelength range of 450 to 650 nm. Eraser friction: Use Eraser Co., Ltd. No. 50, under the load of 1 kg, to go back and forth 50 times on the surface, and visually evaluate the surface damage. It is regarded as 0 when no damage or change is seen. Antifouling property: "Tracey" (registered trademark) manufactured by Toray Co., Ltd. was used to wipe the quick-drying ink ("McGy" (registered trademark) manufactured by Zebra) written on the surface of the film several times to evaluate the wiping state. 〇 is a state where writing marks are completely erased, △ is a state where some are not erased and remains, and X is a state where most of them are left.) -35- 1225159 V. Description of the invention (34) Screen viewing ease: visually evaluate fluorescent light Ease of viewing when the lamp is reflected (0 is difficult to see the reflected person, X is the person who sees the reflected person, △ is the middle). Fingerprint erasability: The fingerprint on the surface is made by Toray Corporation. "Tracey" (registered trademark) evaluate the ease of wiping off several times (0 is a light force to wipe off a few times, X is a force to wipe off, △ is the middle case). Injury resistance: use # 〇〇〇〇Wire wool, under the load of 1.96N / cm2, slightly rub the surface of the hard coating film, visually observe the number of times when a flaw occurs. Inventive effect When the surface of the hard coating layer elastic modulus and thickness three times When the square product is 30KPa * mm3 to 700KPa · mm3 Then, a hard coating film with high pencil hardness and hard surface damage can be obtained. Brief Description of the Drawings Figure 1 shows the layer structure of one embodiment of the hard coating film of the present invention. Figure 2 shows the attachment of the present invention. A layer structure of one embodiment of a hard coating film of an organic thin film. Fig. 3 shows a sectional view of an image display device provided with the hard coating film of the present invention or a hard coating film with a functional film. Fig. 4 is a sectional view of an image display device provided with a base material laminated with a hard coating film or a hard coating film with a functional film according to the present invention. Explanation of Symbols -36- 1225159 V. Description of the Invention (35) 1 base Material film 2 Hard coating layer 3 a High refractive index layer 3b Low refractive index layer 4 Antistatic undercoating A Image display device B Substrate C Hard coating film or hard coating film with organic film -37-

Claims (1)

1225159 Sixth, the scope of application for patents No. 9 1 1 09 5 99 "Patent for hard coating, substrate with laminated hard coating, and some image display devices" (revised on December 16, 1992 6. Scope of patent application: 1 · A hard coating film, which is formed by laminating a hard coating layer on at least one side of a base film, which is characterized by: the surface elastic modulus and the hard coating of the hard coating layer The cubic product of the layer thickness is 30KPa * mm3 to 700KPa * mm3. The hard coating layer is repeated by a monomer, oligomer or polymer containing a polyfunctional polymerizable unsaturated double bond group and containing the formula (1). The composition of the crosslinkable polymer of the unit passes through the double bond group in the monomer, oligomer, or polymer containing the polyfunctional polymerizable unsaturated double bond group and the repeating unit containing the repeating unit represented by the formula (1). It is formed by the polymerization of both the ring-opening polymerizable groups in the crosslinkable polymer and the hardened composition formed by hardening. Formula (1) / f-(-ch2-c- ^ P1 where R1 represents a hydrogen atom or For radicals having 1 to 4 carbon atoms, pi is a monovalent radical containing a ring-opening polymerizable group, and L1 is a single or divalent linking group. 2 · For example, the hard-coated film of the scope of patent application, where pi is a monovalent group containing an epoxy ring, azetidine ring, and Doxa ring. 3. As of the scope of patent application, item 1 Hard coating film, wherein the hard coating 1225159 6. The surface elastic modulus of the patent-applied layer is 4.0 GPa to 9.0 GPa. 4. The hard coating film according to item 1 of the patent application scope, wherein the hardening composition is The volume shrinkage after hardening is 0 to 15%. 5. The hard coating film according to item 1 of the patent application scope, wherein the hardened I / O 値 of the hardening composition is 0.3 to 0.85. 6. If applied The hard coating of item 1 of the patent scope, in which the curl of the hard coating (curl 値 = 1 / R (R is the radius of curvature (m)) is between -15 and 25 ° C at 60% RH). Within the range of +15. 7. If the hard coating film in the first item of the patent application scope, the absolute difference between the curling difference between 25 ° C 80% RH and 25 ° C 10% RH is 24 or less. 8. The hard coating film with an organic thin film as described in item 1 of the scope of patent application, which is a functional film with anti-reflection or antifouling function laminated on the hard coating layer. A substrate laminated with a hard coating film according to any one of claims 1 to 8. 1 0 · —A hard coating film having any one of claims 1 to 8 An image display device. 1 1 · An image display device provided with a base material laminated with a hard coating film according to any one of claims 1 to 8.