TWI750226B - Hard coat film for adhering inorganic compound layer, and transparent conductive film and touch panel using the hard coat film - Google Patents

Abstract

The present invention aims to provide a hard coat film having a hard coat layer capable of improving adhesion with an inorganic compound layer. In particular, the purpose is to provide a hard coat film which does not change with the passage of time and can maintain good adhesion. The solution is that the hard coat film of the present invention is used to adhere an inorganic compound layer on the hard coat layer. The hard coat layer includes particles modified to be reactive and a binder resin, and the content of the particles is 1 part by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the solid content of the binder resin.

Description

Hard coat film for following inorganic compound layer, and transparent conductive film and touch panel using the hard coat film

[0001] The present invention relates to a hard coat film having a hard coat layer for adhering an inorganic compound layer, which is suitable for electrode films, gas barrier films, and the like.

The electrode film used in the touch panel is formed by sputtering on the hard coat layer laminated on the surface of the transparent substrate to form an ITO (tin-doped indium oxide) film, and an electrode is formed on the ITO film by etching pattern made. Patent Document 1 discloses a technique of forming a transparent conductive layer such as ITO on a hard coat layer, such that the layer has a hard coat film with good adhesion. However, in the electrode film in which the ITO film is formed on the hard coat layer, there is a difference in optical characteristics (transmittance, hue, reflectance, etc.) between the portion where the ITO film is present and the portion where the ITO is removed, and electrode patterning occurs. The phenomenon of revealing, resulting in poor appearance. Therefore, in recent years, the electrode film system adopts a structure in which an optical adjustment layer for adjusting optical properties is arranged between the hard coat layer and the ITO film. Thereby, the difference between the optical characteristics of the part where the ITO film is present and the optical characteristics of the part where the ITO film is removed and the optical adjustment layer is exposed becomes smaller, and the electrode pattern becomes less conspicuous. [Prior Art Document] [Patent Document] [0003] [Patent Document 1] Japanese Patent Laid-Open No. 2015-183168

[Problems to be Solved by the Invention] [0004] As described above, the electrode film having the optical adjustment layer between the hard coat layer and the ITO film, since the optical adjustment layer is formed on the hard coat layer by the sputtering method, it is easy to A film having a hard coat layer with good adhesion to the optical adjustment layer is required. In particular, in order to improve the reliability of the electrode film, it is desirable that it is less likely to change with time, and that the adhesion to the optical adjustment layer can be maintained favorably. Although Patent Document 1 discloses that by mixing a predetermined hydrophobized silica gel and a specific leveling agent into the hard coat layer, good adhesion between the hard coat layer and ITO can be achieved, but it is not related to optical adjustment. The continuity of the layers is not revealed or taught in any way. [0006] Therefore, the present invention aims to provide a hard coat film (hereinafter referred to as "hard coat film") having a hard coat layer that can improve adhesion with an inorganic compound layer. In particular, the purpose is to provide a hard coat film which does not change with the passage of time and can maintain good adhesion. [MEANS TO SOLVE THE PROBLEM] [0007] The hard coat film of the present invention is used to adhere an inorganic compound layer on the hard coat layer. The hard coat layer includes particles modified to be reactive and a binder resin, and the content of the particles is 1 part by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the solid content of the binder resin. [0008] Also, in the hard coat film of the present invention, it is preferable that the average particle diameter of the aforementioned particles is 100 nm or more and 1000 nm or less. [0009] Furthermore, in the hard coat film of the present invention, it is preferable that the particle diameter of the primary particles is not less than 1 nm and not more than 100 nm when the particles constitute secondary particles as aggregates of primary particles. [0010] Also, in the hard coat film of the present invention, it is preferable that the aforementioned particles be a combination of two or more of silicon dioxide, aluminum oxide, titanium, zirconium oxide, calcium carbonate, magnesium carbonate, barium sulfate, or these. [0011] Also, in the hard coat film of the present invention, it is preferable that the aforementioned particle system has a combination of two or more of acryl group, hydroxyl group, carboxyl group, amino group, epoxy group, isocyanate group, or these functional groups. Also, the hard coating film of the present invention is preferably based on the value of the bending resistance test of the aforementioned hard coating measured by the cylindrical mandrel method of JIS-K5600-5-1 (1999). 6mm or less. Also, in the hard coat film of the present invention, preferably, in the above-mentioned film lamination inorganic compound layer, and carrying out the hourglass cross-cut peeling test after the boiling treatment, the inorganic compound layer is only partially peeled off by the hard coat layer. or better. [0014] Also, in the hard coat film of the present invention, preferably the aforementioned inorganic compound layer is an optical adjustment layer or a gas barrier layer. [0015] Also, in the hard coat film of the present invention, preferably the inorganic compound is SiO ₂ or Nb ₂ O _x (only 4≦x≦5). [0016] Also, the hard coat film of the present invention, preferably the above-mentioned inorganic compound layer is composed of a single layer or multiple layers. [0017] Also, the transparent conductive film of the present invention is characterized by using the above-mentioned hard coat film of the present invention. [0018] Furthermore, the touch panel of the present invention is characterized by using the above-mentioned hard coat film of the present invention. [Effect of the Invention] [0019] According to the present invention, the adhesion between the inorganic compound layer and the hard coat layer can be improved. In particular, it is unlikely to change with time, and the adhesiveness can be maintained favorably.

[0077] 就接著性之評定，實驗例1～3的膜之初始接著性試驗之對SiO₂ 及Nb₂ O_x (惟4≦x≦5)的接著性，經第1次及第2次剝離全為「無剝離」。又，此等實施例之煮沸後接著性試驗之對SiO₂ 的接著性，經第1次剝離，為「無剝離」，經第二次則為「有部分剝離」或「無剝離」；對Nb₂ O_x (惟4≦x≦5)的接著性，實施例1以外者，經第1次及第2次此兩次剝離全為「無剝離」。 　　另一方面，比較例1的膜對SiO₂ 及Nb₂ O_x (惟4≦x≦5)的接著性之評定，在初始接著性試驗中係較實施例1～3者為差，在煮沸後接著性試驗中為「全部剝離」。 　　此等結果顯示，具有反應性修飾粒子21之實施例1～3的膜，即使在如高溫多濕之嚴峻的環境下，也不易隨時間經過發生變化，可維持初始之對無機化合物層40的接著性。 　　[0078] 就柔軟性，實施例1～3較比較例1更具有柔軟性。從而，可知透過硬塗層20具備適度的柔軟性，可提升對無機化合物層40的接著性。[0021] Hereinafter, with reference to FIGS. 1 to 5, an embodiment of the hard coat film 1 for adhering the inorganic compound layer 40 of the present invention will be described. In addition, as long as the inorganic compound layer 40 is a layer which has an inorganic compound, it may be a layer containing an inorganic compound, and may be a layer of the inorganic compound itself. The hard coat film 1 of the present invention is characterized by having a hard coat layer 20, and the hard coat layer 20 comprises particles (reactive modified particles) 21 and a binder resin 22 modified to have reactivity, and the reactive The content of the modification particles 21 is 1 part by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the binder resin 22 . Embodiment of the present invention, as its basic constitution, is shown in Figure 1 (a), possesses support 10 and the hard coat 20 formed on support 10. The hard coat film 1 is not only the one shown in FIG. 1( a ), but may also be a single-layer hard coat film ( FIG. 1( b )), or may be formed between the support 10 and the surface on which the hard coat layer 20 is formed. The surface on the opposite side is provided with a back coating (FIG. 1(c)). [0024] Such a hard coat film 1 is shown in FIG. 2, and an inorganic compound layer 40 is laminated on the hard coat layer 20. At this time, the hard coat layer 20 has excellent adhesion to the inorganic compound layer 40 . [0025] First, the reactive modified particles 21 and the binder resin 22 constituting the hard coat layer 20 will be described. [0026] The binder resin 22 has a function as a binder for the reactive modified particles 21 to be described later. The binder resin 22 preferably has reactive functional groups. At this time, it is bonded to the reactive functional group of the reactive modified particle 21, and the detachment of the reactive modified particle 21 can be effectively prevented. As a reactive functional group of the binder resin 22, an acryl group, a hydroxyl group, a carboxyl group, an amine group, an epoxy group, an isocyanate group, etc. are mentioned. [0027] As for the binder resin 22, it can be used alone or in combination of two or more kinds of resins such as ionizing radiation curable resin, thermosetting resin, thermoplastic resin, etc., and can be used according to the purpose. Among them, when higher hardness is required, ionizing radiation curing resin is preferably used. As ionizing radiation curable resin, can enumerate by irradiating ionizing radiation (ultraviolet or electron beam) to achieve cross-linking and hardening of resin, it is particularly preferable to use, for example, 1 or 2 or more ( Meth)acryloyl acrylic resin. Examples of the acrylic compound include urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, melamine (meth)acrylate, and polyfluoroalkane. base (meth)acrylate, siloxane (meth)acrylate, etc. As the thermosetting resin, for example, polyester acrylate-based resin, polyurethane acrylate-based resin, epoxy acrylate-based resin, epoxy-based resin, melamine-based resin, and phenol-based resin can be cited , polysiloxane resin, etc. As thermoplastic resin, for example, polyester-based resin, acrylic resin, polycarbonate-based resin, cellulose-based resin, acetal-based resin, vinyl-based resin, polyethylene-based resin, polystyrene-based resin can be enumerated Resin, polypropylene resin, polyamide resin, polyimide resin, fluorine resin, etc. [0031] Also, the binder resin 22 preferably contains a certain amount of high molecular weight resin. By combining the high molecular weight resin and the reactive modified particles 21 described later, a certain degree of flexibility can be imparted to the hard coat layer 20 without impairing the hardness, and the anchoring of the inorganic compound layer 40 to the hard coat layer 20 can be improved. effect. Thereby, the adhesion between the hard coat layer 20 and the inorganic compound layer 40 can be further improved. The high molecular weight resin refers to a resin having a weight average molecular weight (Mw) of 10,000 or more, preferably 10,000 to 150,000, and more preferably 30,000 to 100,000. The high molecular weight resins may be used alone or in combination of two or more types of resins such as ionizing radiation curable resins, thermosetting resins, thermoplastic resins, and the like. Examples of the ionizing radiation curable resin, thermosetting resin, and thermoplastic resin are the same as those listed above as examples of the ionizing radiation curable resin, thermosetting resin, and thermoplastic resin as the binder resin 22 . The content thereof is 1 part by weight or more and 50 parts by weight or less, more preferably 5 parts by weight or more and 40 parts by weight or less, relative to 100 parts by weight of the binder resin 22 (solid content). In addition, when the binder resin 22 contains a high molecular weight resin, "the binder resin 22 (solid content)" refers to the solid content of the entire binder resin 22 containing the high molecular weight resin. [0032] The reactive modified particles 21 contribute to improving the adhesion of the hard coat layer 20 to the inorganic compound layer 40 and maintaining the adhesion over time. The reactive modified particle 21 is a particle in which a reactive functional group is imparted to the surface of the inorganic particle by modifying the surface of the inorganic particle. The reactive functional groups are bonded to the reactive functional groups of the binder resin 22 to prevent the reactive modified particles 21 from falling off from the hard coat layer 20 . Furthermore, it is presumed that by having a reactive functional group, the adhesion to the inorganic compound layer can be maintained under high temperature and high humidity conditions. Examples of the inorganic particles include silica, alumina, titanium, zirconia, calcium carbonate, magnesium carbonate, barium sulfate, and the like, and these inorganic particles may be used alone or in combination of two or more. As a reactive functional group, an acryl group, a hydroxyl group, a carboxyl group, an amine group, an epoxy group, an isocyanate group etc. are mentioned, for example, These reactive functional groups can be used individually or in combination of 2 or more types. The content of the reactive modified particles 21, in order to exert the adhesion to the inorganic compound layer 40, the lower limit of the reactive modified particles 21 is 1 with respect to 100 parts by weight of the binder resin 22 (solid content). The weight part or more is preferably 3 weight parts or more, more preferably 5 weight parts or more, and most preferably 10 weight parts or more. On the other hand, the upper limit of the reactive modified particles 21 is not particularly limited, but is 60 parts by weight or less, preferably 40 parts by weight or less, more preferably 30 parts by weight relative to 100 parts by weight of the binder resin 22 (solid content). parts by weight or less. When the content of the reactive modified particles 21 is less than the above-mentioned range, the adhesion with the inorganic compound layer 40 tends to be weakened. On the other hand, when it exceeds the said range, it will become difficult to maintain transparency, and it will become unfavorable. [0034] As long as the reactive modified particles 21 are of a predetermined size, they can be primary particles or secondary particles belonging to aggregates; and in order to further obtain adhesiveness, they are preferably secondary particles. The reason why the adhesion is more improved when secondary particles that are aggregates of primary particles are used as the reactive modification particles 21 compared to the case where only primary particles of the same size are used is not known, but it is considered that the particles protrude toward the surface. This is due to the increase in the contact area with the inorganic compound layer 40 . The average particle diameter of the reactive modified particles 21 (including secondary particles in the form of primary particles or aggregates of primary particles) varies with the thickness of the hard coat layer 20 and cannot be generalized, but the lower limit is 100 nm or more. It is preferably 110 nm or more, more preferably 130 nm or more. Moreover, the upper limit is 1000 nm or less, preferably 800 nm or less, and more preferably 600 nm or less. Furthermore, in the above, when the reactive modified particles 21 are composed of secondary particles that are aggregates of primary particles, the lower limit of the average particle diameter of the primary particles that are the constituents of the secondary particles is 1 nm or more. , preferably 20 nm or more, more preferably 30 nm or more. Moreover, the upper limit is 100 nm or less, preferably 80 nm or less, and more preferably 60 nm or less. Adhesion to the inorganic compound layer 40 can be obtained by setting the average particle diameter of the reactive modified particles 21 or the average particle diameter of the primary particles when the reactive modified particles 21 are composed of secondary particles to be equal to or larger than the above lower limit value. On the other hand, by making these average particle diameters into each of the said upper limit or less, the translucency which can be used for transparent use can be obtained. In addition, the average particle diameter of a particle means the value of the volume average particle diameter (D50) which can be measured by the laser diffraction/scattering method. [0035] The hard coat layer 20 may further contain a photoinitiator, a curing agent, and the like depending on the curing method. Examples of the photoinitiator include acetophenones, benzophenones, Michler's ketone, benzoin, benzyl methyl ketal, benzyl benzoate, α-acyl oxime ester, thiol Photo-radical polymerization initiators such as xanthones, or photocationic polymerization initiators such as onium salts, sulfonic acid esters, and organometallic complexes. Moreover, as a hardening|curing agent, compounds, such as a polyisocyanate, an amine resin, an epoxy resin, a carboxylic acid, can be used suitably by mix|blending suitable resin. In the hard coat layer 20, within the scope of not impairing the performance, in addition to the above-mentioned binder resin, polymer resin, reactive modified particles, photoinitiator, hardener, antistatic agent, Additives for dispersants, flocculants, UV absorbers, antioxidants, levelers, etc. The thickness of hard coat 20 (referring to the L of Fig. 1 (a)), when hard coat 1 has support 10, is 0.1～10.0 μm, preferably 0.5～5.0 μm, more preferably 1.0～1.0 μm 3.0 μm. Moreover, when the hard coat film 1 is provided with the back coat layer 30 in addition to the support body 10, it is 0.1-10.0 micrometers, Preferably it is 1.0-5.0 micrometers, More preferably, it is 1.0-3.0 micrometers. By having such a thickness, the adhesion between the hard coat layer 20 and the inorganic compound layer 40 can be improved. In addition, in the case of a single hard coat layer, the thickness thereof is 0.1 to 10.0 μm, preferably 0.5 to 5.0 μm, and more preferably 1.0 to 3.0 μm. By setting the thickness to 0.1 μ or more, the adhesion to the inorganic compound layer 40 can be obtained, and the strength of the coating film can be more sufficient, and the handleability can be improved. The thickness of the hard coat layer 20 was measured using a reflection spectrometer (Otsuka Electronics FE-300). Next, the support body 10 when the hard coat film 1 has the support body 10 is explained. The support 10 can be used without particular limitation as long as it is a plastic film with high optical transparency. For example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polycycloolefin, polyethylene, polycarbonate, polypropylene, polyphenylene can be used Ethylene, cellulose triacetate, acrylic acid, polyvinyl chloride, norbornene compounds, etc. Among them, a polyethylene terephthalate film that has been stretched, especially biaxially stretched, is preferred because of its excellent mechanical strength or dimensional stability. Moreover, in order to improve the adhesiveness with the hard-coat layer 20, it is also preferable to use the thing which performed the corona discharge treatment on the surface, or provided the easy-adhesion layer. In addition, the thickness of the support body 10 is usually preferably about 6 to 250 μm, and more preferably about 23 to 188 μm. The support 10 preferably has light transmittance, and specifically, the total light transmittance (JISK7136) is 85% or more, preferably 90% or more. Again, hard coat film 1 can also be as above-mentioned, and is further provided with back coat layer 30 (Fig. 1 (c)) on the opposite side of support body 10 with hard coat layer 20. At this time, the back coat layer 30 is not particularly limited, and can be selected from a hard coat layer, an adhesive layer, an antistatic layer, etc., and may also include the above-mentioned hard coat layer 20 . The making method of hard coat film 1 is not particularly limited, for example, when having support 10, can make the material of above-mentioned hard coat 20 dissolve or be dispersed in the hard coat coating liquid that suitable solvent forms. , coated on the support by a known method such as bar coating, dried, and irradiated with ultraviolet rays as required. In addition, by forming a mold release layer on the support 10 in advance, after forming the hard coat layer 20 on the support 10, the support 10 is peeled off and removed to form a film composed of a single hard coat layer. Also, in the case of the hard coat film 1 having the back coat layer 30, the surface of the support 10 having the hard coat layer 20 on the opposite side to the hard coat layer 20 may be coated by a known method such as bar coating. The cloth is dissolved or dispersed in a coating liquid for a back coat layer formed by an appropriate solvent, dried, and produced by irradiating ultraviolet rays as needed. [0041] Next, the characteristics of the hard coat layer 20 will be described. The properties that the hard coat layer 20 should have are adhesion and flexibility. First of all, the adhesion can be, for example, in the state where the inorganic compound layer is laminated without any treatment (hereinafter referred to as "initial adhesion test") and the state after boiling treatment which is a test for promoting weather resistance (hereinafter referred to as "the initial adhesion test"). "Adhesion test after boiling") The hourglass cross-cut peeling test was carried out in these two states, and the quality was judged and evaluated according to the results. The hourglass cross-cut peeling test is performed by cross-cutting the surface of the inorganic compound layer 40 into an hourglass-like shape, as described later, and therefore, the adhesiveness can be evaluated under conditions more severe than cross-cutting in a checkerboard shape. . Here, the initial adhesion test method (hourglass cross-cut peeling test method) is as follows. [0044] The hard coating film 1 is sputtered with an inorganic compound (such as SiO ₂ , Nb ₂ O _x (4≦x≦5), etc.), and a test piece (test piece) having an inorganic compound layer 40 with a thickness of about 200 nm is formed. production steps). [0045] Next, as shown in FIG. 3 , the surface of the inorganic compound layer 40 is scribed in a manner that the line segment DD' and the line segment EE' are parallel, and the width between these line segments is 2 cm. Next, the line segments FF' and GG' intersect with each other, one end of the line segments FF' and GG' respectively intersect with the line segment DD', and the other ends of the line segments FF' and GG' respectively intersect with the line segment EE'. The surface of the inorganic compound layer 40 is scratched. At this time, the incision was drawn so that the two triangles ABC and AB'C' formed by the line segments DD', EE', FF', and GG' formed an isosceles triangle with an apex angle of 30 degrees and a height of 1 cm. Here, the point where the line segment FF´ and the line segment GG' intersect is taken as the vertex A, the intersection point of the line segment GG' and the line segment FF' on the line segment DD' is taken as the point B and the point C respectively, and the line segment GG on the line segment EE' The intersection points of ' and line segment FF' are point B' and point C' respectively (cutting step). The tape (Nichiban, Cellotape (registered trademark)) was applied so as to cover the two isosceles triangles formed by the cut marks, and the pasted tape was torn off at a predetermined angle and speed (the first time). stripped). Next, with respect to the test piece after the 1st peeling, the peeling test (2nd peeling) was similarly performed again in the same place where the 1st peeling was performed using the newly prepared tape. In addition, it carried out according to the cross-cut method prescribed|regulated to JISK5600-5-6 except the said dicing method and peeling twice continuously at the same place (peeling step). [0047] The test is carried out according to the initial adhesion test method. In the present invention, the adhesion of the hard coat layer is preferably the second peeling, and the inorganic compound layer 40 is not peeled off from the hard coat layer 20 at all. By having such adhesiveness, the time-lapse adhesiveness to the inorganic compound layer 40 can be improved. Furthermore, the difference between the adhesion test method after boiling and the initial adhesion test method is that after the test piece making step of the initial adhesion test method described above, there is a test piece making step before the cutting step. The test piece obtained in the process of boiling treatment with pure water for a predetermined period of time (boiling treatment step). In addition, as for the boiling treatment step, when the inorganic compound layer 40 is SiO ₂ , it is boiled for 6 hours. In addition, when the inorganic compound layer 40 is Nb ₂ O _x (only 4≦x≦5), it is boiled for 1 hour. The test is carried out according to the test method for adhesion after boiling. In the present invention, the adhesion of the hard coat layer is preferably peeled off for the first time or the second time, and the inorganic compound layer 40 is only composed of 20 parts of the hard coat layer. peeled off or better than this; more preferably, better than the first or second peeling, the inorganic compound layer 40 is only partially peeled off from the hard coat layer 20; more preferably after the second peeling , the inorganic compound layer 40 is not peeled off by the hard coat layer 20 at all. By having such adhesiveness, the adhesiveness to the inorganic compound layer 40 under high temperature and high humidity can be improved. Alternatively, when combining the initial adhesion test and the boiling back adhesion test method, in the present invention, with regard to the adhesion of the hard coat layer 20, it is preferable to peel off the inorganic compound for the second time than the initial adhesion test. If the layer 40 is not peeled off from the hard coat layer 20 at all, and the first peeling of the adhesion test after boiling, the inorganic compound layer 40 is only partially peeled off from the hard coat layer 20. Better; better than the initial adhesion test In the second peeling, the inorganic compound layer 40 was not peeled off from the hard coat layer 20 at all, and the second peeling of the post-boiling adhesion test, the inorganic compound layer 40 was only partially peeled off from the hard coat layer 20. By having such adhesiveness, even in severe environments such as high temperature and high humidity, it is not easy to change with the passage of time, and the initial adhesiveness can be maintained. [0051] In addition, the softness properties of the hard coat layer 20 were evaluated in a bending resistance test. The value of the bending resistance test varies depending on the material or thickness of the hard coat layer 20, or, when the hard coat film 1 has the support 10 and the back coat layer 30, depending on the type or thickness of those, therefore, in In this specification, as a support, a PET film with a film thickness of 125 μm “KFL10W” manufactured by Teijin Du Pont Co., Ltd. with an easily adhesive bond was used, and the bending resistance test was carried out on the condition that no layers other than the easily bondable layer were laminated on the back surface. . In the present invention, the value of the bending resistance test (diameter of the iron rod at which cracks first occurred in the hard coat layer or peeled off from the support) is preferably 6 mm or less, more preferably 2 mm or less. By setting the value of the bending resistance test to be equal to or less than a predetermined value, the hard coat layer 20 has flexibility, and the adhesiveness to the inorganic compound layer 40 can be improved. In addition, the value of the bending resistance test is the value measured by the cylindrical mandrel method based on JIS-K5600-5-1 (1999). Next, the optical properties that the hard coat film 1 of the present invention should possess will be described. [0053] Regarding the optical properties of the hard coat film 1, the total light transmittance (JISK7136) is preferably 85% or more, more preferably 90% or more. By having such light transmittance, it is possible to impart adhesiveness to the inorganic compound layer 40 without impairing the visibility of the display device etc. to which the hard coat film 1 is attached. The haze (JISK7136) of the hard coat film 1 is preferably 4.0% or less, more preferably 2.0% or less, still more preferably 1.0% or less, and most preferably 0.8% or less. By adjusting the content according to the average particle size of the particles, a suitable haze can be maintained. Next, take the hard coat film 1 of the structure shown in FIG. 1(a) as an example to illustrate the application example of the hard coat film 1. FIG. 2 shows an example of the hard coat film (laminate) 2 in which the inorganic compound layer 40 is laminated. The laminate 2 is formed by adhering the inorganic compound layer 40 to the hard coat layer 20 of the hard coat film 1 to form a laminate. [0056] As the inorganic compound layer 40, an optical adjustment layer 50 or a gas barrier layer 51 can be mentioned. When the optical adjustment layer 50 is laminated on the hard coat layer 20 , the hard coat film 1 can be used for the optical adjustment layer-attached film 3 ( FIG. 2 ). Furthermore, as shown in FIG. 4( a ), by further laminating the transparent conductive film 60 on the optical adjustment layer 50 , the hard coat film 1 of the present embodiment can be used for the transparent conductive film 4 . The film 3 with an optical adjustment layer and the transparent conductive film 4 can be used as electrode sheet members of an electrostatic capacitance type or resistive film type touch panel. [0057] As the inorganic compound of the optical adjustment layer 50, as long as it is used to adjust the optical properties of the transparent conductive film 60, SiO ₂ , Nb ₂ O _x (only 4≦x≦5) and the like can be cited. In addition, the optical adjustment layer 50 can be constituted by a single layer or a plurality of layers. In the case of a single layer, as shown in FIG. 5( a ), as the optical adjustment layer 50 , for example, a SiO ₂ film is formed on the hard coat layer 20 . In the case of multiple layers, as shown in FIG. 5( b ), for example, a Nb ₂ O _x (only 4≦x≦5) film and a SiO ₂ film are sequentially laminated on the hard coat layer 20 . The lamination of SiO ₂ or Nb ₂ O _x (only 4≦x≦5) can be a conventionally known method, and a film is formed by a sputtering method or an evaporation method. As the transparent conductive film 60, those composed of tin-doped indium oxide (ITO), zinc oxide (ZnO), aluminum-doped zinc oxide (AZO), silver, copper or copper alloy, carbon nanotubes, etc. can be mentioned. membrane. The lamination of the transparent conductive film 60 may be a conventionally known method, and the film may be formed by a sputtering method such as DC sputtering or RF sputtering, or a vapor deposition method. When used in an electrostatic capacitance type touch panel, an etching process is performed on the formed transparent conductive film 60 to form a desired electrode pattern (FIG. 4(b)). When such an electrode pattern is formed, the optical adjustment layer 50 serves to make the electrode pattern invisible. For example, in the case of the transparent conductive film 4 having an ITO electrode pattern, as shown in FIG. 4( b ), the optical adjustment layer 50 can reduce the light 71 reflected by the removed portion of ITO and the light 70 reflected by the remaining portion of ITO The difference in optical properties (reflectivity, hue, transmittance, etc.) makes the ITO electrode pattern difficult to see. [0059] On the other hand, when the gas barrier layer 51 is laminated on the hard coat layer 20, the hard coat film 1 can be used as a gas barrier film 5 suitable for EL displays, EL lighting, solar cells, and the like (FIG. 2). Examples of the inorganic compound of the gas barrier layer 51 include magnesium, titanium, aluminum, indium, silicon, tin, and oxides thereof, and these may be used alone or in combination of two or more. From the viewpoint of workability or cost, aluminum or alumina is preferably used. Lamination of the gas barrier layer 51 on the hard coat layer 20 may be performed by a conventionally known method, and may be formed by sputtering or vapor deposition. [0060] According to the hard coat film 1 of the present invention, the adhesion of the hard coat layer 20 to the inorganic compound layer 40 can be improved. In particular, it is unlikely to change with time, and the adhesiveness can be maintained favorably. [Examples] [0061] Examples of the protective film of the present invention will be described below. In addition, in the following examples, unless otherwise stated, "%" and "part" are based on weight. <Example 1> The coating liquid for hard coating of the following formula was applied to one side of a polyethylene terephthalate film (KFL10W, manufactured by Teijin Du Pont) with a thickness of 125 μm, dried, and then irradiated. It was hardened with ultraviolet rays to form a hard coat layer having a thickness of 2.0 μm, and the hard coat film of Example 1 was prepared. <Coating liquid for hard coating> ・Binder resin 30 parts of ionizing radiation curing resin (UNIDIC 17-813: DIC company, solid content 80%) 15 parts of high molecular weight resin (ACRYDIC A195: DIC company, solid content Content 40%) (weight average molecular weight: 85000) ・15 parts of reactive modified particle dispersion (SIRMIBK30WT%-M06: CIK NanoTek, solid content 30%) (Silicon dioxide particles: average primary particle size 30 nm, average secondary particle size Particle size 200-300nm) ・60 parts of dilution solvent ・0.4 part of photoinitiator (IRGACURE 184: BASF Corporation) The protective film of Example 2 was produced in the same manner as in Example 1 except that the parts by weight were changed to 30. <Example 3> The protective film of Example 3 was prepared in the same manner as in Example 1, except that the weight parts of the reactive modified particles in the coating solution for hard coating of Example 1 were changed to 60 . <Comparative Example 1> A protective film of Comparative Example 1 was prepared in the same manner as in Example 1 except that the reactive modified particles in the coating liquid for hard coating of Example 1 were removed. [0067] The following properties were evaluated for the protective films manufactured in the above-described examples and comparative examples. 1. optical properties follow JISK7136 measuring method, by haze meter (Suga Test Instruments company, type HGM-2K), color computer (Suga Test Instruments company, type SM-4), with the hard coating of each protective film The layer was the light incident surface, and the total light transmittance (Tt) and the haze (Haze) were measured. 3. Regarding "bending resistance", based on the bending resistance (cylindrical mandrel method) according to JIS-K5600-5-1 (1999), prepare iron rods with diameters of about 3 mm and 7 mm, and use Each iron rod was folded and wound with the hard coat layer attached with the hard coat layer 20 on the outside, and the hard coat layer 20 at the wound portion was visually observed for cracking or peeling off from the support. As a result, those who could not confirm cracks or peel off from the support with a 3 mm iron rod were rated as "○"; with a 3 mm iron rod, although cracks or peeling from the support were confirmed with a 3 mm iron rod, they could not be confirmed with a 7 mm iron rod. Those with cracks or peeling off of the support were rated as "△"; those with any type of iron bars were identified as cracks or peeled off from the support, and rated as "X". 4. Initial Adhesion Test (Hourglass Cross Cut Peeling Test) On the hard coat layer of the hard coat film manufactured in the above-mentioned embodiment and the comparative example, with a sputtering device (manufactured by SHIBAURA MECHATRONICS: CFS-4EP-LL ) by sputtering SiO ₂ or Nb ₂ O _x (only 4≦x≦5) to prepare a test piece having an inorganic compound layer 40 having a thickness of about 200 nm (test piece production step). [0071] Next, as shown in FIG. 3 , a notch is drawn on the surface of the inorganic compound layer 40 in a manner that the line segment DD' and the line segment EE' are parallel, and the width between these line segments is 2 cm. Next, the line segments FF' and GG' intersect with each other, one end of the line segments FF' and GG' respectively intersect with the line segment DD', and the other ends of the line segments FF' and GG' respectively intersect with the line segment EE'. The surface of the inorganic compound layer 40 is scratched. At this time, the incision was drawn so that the two triangles ABC and AB'C' formed by the line segments DD', EE', FF', and GG' formed an isosceles triangle with an apex angle of 30 degrees and a height of 1 cm. Here, the point where the line segment FF' and the line segment GG' intersect is the vertex A, the intersection point of the line segment GG' and the line segment FF' on the line segment DD' is the point B and the point C, respectively, and the line segment GG' on the line segment EE' The intersection points of ' and line segment FF' are point B' and point C' respectively (cutting step). A tape (Nichiban, Cellotape (registered trademark)) was applied so as to cover the two isosceles triangles formed by the cut marks, and the pasted tape was torn off at a predetermined angle and speed (the first time). stripped). Next, with respect to the test piece after the 1st peeling, the peeling test (2nd peeling) was similarly performed again in the same place where the 1st peeling was performed using the newly prepared tape. In addition, it carried out based on the cross-cut method prescribed|regulated to JISK5600-5-6 except the said dicing method and peeling twice continuously at the same place (peeling step). In this peeling test, the inorganic compound layer 40 is rated as ○ (no peeling) by those who are not peeled off from the hard coat layer 20 at all; the inorganic compound layer 40 is rated as △ (partially peeled off by the hard coat layer 20 peeling); almost all of the inorganic compound layer 40 peeled off from the hard coat layer 20 was rated as × (all peeled off). 5. Test method for adhesion after boiling When the inorganic compound layer is SiO ₂ , after the test piece preparation step of the initial adhesion test described above, the test piece is boiled with pure water for 6 hours (boiling treatment step). Next, the cutting step and the peeling step described above are performed, and the case where the inorganic compound layer 40 is not peeled off from the hard coat layer 20 at all is rated as ○ (no peeling); the case where the inorganic compound layer 40 is partially peeled off from the hard coat layer 20 is rated as Δ ( Partial peeling); almost all of the inorganic compound layer 40 peeled off from the hard coat layer 20 was rated as × (complete peeling). When the inorganic compound layer was Nb ₂ O _x (only 4≦x≦5), the test and evaluation were carried out in the same manner as in the case of _{SiO 2} above except that in the above boiling treatment step, the boiling time was 1 hour. The results are shown in Table 1. [0076]

_{As for the evaluation of the adhesion, the adhesion to SiO 2} and Nb ₂ O _x (only 4≦x≦5) of the initial adhesion test of the films of Experimental Examples 1 to 3, after the first and second times Stripping is all "no stripping". _{In addition, the adhesion to SiO 2} in the adhesion test after boiling of these examples is "no peeling" after the first peeling, and "partial peeling" or "no peeling" after the second peeling; The adhesiveness of Nb ₂ O _x (only 4≦x≦5), except for Example 1, was “no peeling” after the first and second peeling. On the other hand, the evaluation of the adhesion of the film of Comparative Example 1 to SiO ₂ and Nb ₂ O _x (only 4≦x≦5) was inferior to that of Examples 1 to 3 in the initial adhesion test. In the post-adhesion test, it was "all peeled off". These results show that the films of Examples 1 to 3 having the reactive modified particles 21 are not easily changed over time even in severe environments such as high temperature and high humidity, and can maintain the initial adhesion to the inorganic compound layer 40 . Continuity. In terms of flexibility, Examples 1 to 3 are more flexible than Comparative Example 1. Therefore, it can be seen that the transparent hard coat layer 20 has moderate flexibility, and the adhesiveness to the inorganic compound layer 40 can be improved.

[0079] 1‧‧‧Hard coating film 20‧‧‧Hard coating layer 21‧‧‧Reactive modified particles 22‧‧‧Binder resin 40‧‧‧Inorganic compound layer 50‧‧‧Optical adjustment layer 51‧‧‧ gas barrier

Fig. 1 (a) is a sectional view showing an example of the embodiment of the hard coating film of the present invention; (b) is a sectional view showing another example of the embodiment of the hard coating film of the present invention; (c) is A cross-sectional view showing still another example of the embodiment of the hard coat film of the present invention. FIG. 2 is a cross-sectional view showing an example of a hard coat film in which an inorganic compound layer is laminated. FIG. 3 is a plan view illustrating the shape of the cut in the hourglass cross-cut peel test. 4(a) is a cross-sectional view showing an example of a transparent conductive film to which the hard coat film of the present invention is applied; (b) is a cross-sectional view illustrating the transparent conductive film of (a) after the transparent conductive film is etched and the structure of the transparent conductive film A graph of light reflected by a transparent conductive film. Fig. 5(a) is a cross-sectional view of the hard coat film of the present invention _{with a SiO 2 film laminated on the hard coat layer; (b) Nb 2} O _x (only 4≦x≦5) is sequentially laminated on the hard coat layer ) film and the cross-sectional view of the hard coat film of the present invention of the _{SiO 2 film.}

1‧‧‧Hard coating

10‧‧‧Support

20‧‧‧Hard coating

21‧‧‧Reactive Modified Particles

22‧‧‧Binder resin

30‧‧‧Back Coating

L‧‧‧Thickness of hard coating

Claims (12)

A hard coat film having a hard coat layer for adhering an inorganic compound layer, characterized in that: the hard coat layer comprises particles modified to have reactivity and a binder resin, and the content of the particles is , with respect to 100 parts by weight of the solid content of the aforementioned binder resin is 1 part by weight to 60 parts by weight, and the hard coat layer measured according to the cylindrical mandrel method of JIS-K5600-5-1 (1999) The value of the bending resistance test is 6mm or less. A hard coat film having a hard coat layer for adhering an inorganic compound layer, characterized in that: the hard coat layer comprises particles modified to have reactivity and a binder resin, and the content of the particles is , with respect to 100 parts by weight of the solid content of the binder resin, 1 part by weight to 60 parts by weight, and in the hourglass cross-cut peeling test after laminating the inorganic compound layer on the film and performing the boiling treatment, the inorganic compound layer Only partially peeled off by the hard coat or better. The hard coat film according to claim 1 or 2, wherein the average particle diameter of the particles is 100 nm or more and 1000 nm or less. The hard coat film according to claim 1 or 2, wherein when the particles constitute secondary particles as aggregates of primary particles, the particle diameter of the primary particles is 1 nm or more and 100 nm or less. The hard coat film according to claim 1 or 2, wherein the particles are inorganic particles and are silicon dioxide, aluminum oxide, titanium, zirconium oxide, calcium carbonate, magnesium carbonate, barium sulfate, or two or more of these. combination. The hard coat film according to claim 1 or 2, wherein the particles have an acryl group, a hydroxyl group, a carboxyl group, an amine group, an epoxy group, an isocyanate group, or a combination of two or more of these functional groups. The hard coat film according to claim 2, wherein the value of the bending resistance test of the hard coat layer measured by the cylindrical mandrel method according to JIS-K5600-5-1 (1999) is 6 mm or less. The hard coat film according to claim 1 or 2, wherein the inorganic compound layer is an optical adjustment layer or a gas barrier layer. The hard coat film according to claim 1 or 2, wherein the inorganic compound layer is SiO ₂ or Nb ₂ O _x (only 4≦x≦5). The hard coat film according to claim 1 or 2, wherein the inorganic compound layer is composed of a single layer or multiple layers. A transparent conductive film using the hard coat film according to any one of claims 1 to 10. A touch panel using the hard coat film according to any one of claims 1 to 10.

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