KR102406367B1 - Hardcoat film for adhering a layer of inorganic compound, and transparent conductive film and touch panel using the hardcoat film - Google Patents

Abstract

An object of the present invention is to provide a hard coat film having a hard coat layer with improved adhesion with an inorganic compound layer. In particular, an object of the present invention is to provide a hard coating film having good adhesion with little change over time.
In the hard coating film of the present invention, an inorganic compound layer is adhered to the hard coating layer. The hard coating layer includes particles modified to have reactivity and a binder resin, and the content of the particles is 1 part by weight or more and 60 parts by weight or less based on 100 parts by weight of the binder resin solid content.

Description

Hardcoat film for adhering a layer of inorganic compound, and transparent conductive film and touch panel using the hardcoat film

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

The electrode film used for the touch panel is produced by forming an ITO (tin-doped indium oxide) film by sputtering on the hard coating layer laminated on the surface of a transparent substrate, and forming an electrode pattern on the ITO film by etching.

Patent Document 1 discloses a technique of a hard coating film having good adhesion in the case of forming a transparent conductive layer such as ITO on the hard coating layer.

However, in the case of an electrode film in which ITO is formed on the hard coating layer, there is a difference in optical properties (transmittance, color, reflectance, etc.) in the portion where the ITO film is present and the portion where ITO is removed, resulting in the appearance of the electrode pattern. it gets worse For this reason, in recent years, the electrode film has come to employ|adopt the structure which arrange|positions the optical adjustment layer which adjusts an optical characteristic between a hard-coat layer and an ITO film|membrane. Accordingly, the difference between the optical characteristics in the portion where the ITO film is present and the optical characteristic in the portion where the ITO film is removed and the optical adjustment layer is exposed becomes small, and the electrode pattern becomes inconspicuous.

Japanese Patent Laid-Open No. 2015-183168

As described above, in the case of an electrode film having an optical adjustment layer between the hard coating layer and the ITO film, since the optical adjustment layer is formed on the hard coating layer by sputtering, having a hard coating layer with good adhesion to the optical adjustment layer You need a film. In particular, in order to improve the reliability of an electrode film, it is desired that there are few changes with time, and adhesiveness with an optical adjustment layer is maintained favorable.

Patent Document 1 discloses good adhesion between the hard coat layer and ITO by blending a predetermined hydrophobized silica gel and a specific leveling agent in the hard coat layer, but neither disclosure nor suggestion is made regarding the adhesion of the optical adjustment layer.

Accordingly, an object of the present invention is to provide a hard coating film (hereinafter, “hard coating film”) having a hard coating layer having improved adhesion with the inorganic compound layer. In particular, an object of the present invention is to provide a hard coating film having good adhesion properties due to little change over time.

In the hard coating film of the present invention, an inorganic compound layer is adhered on the hard coating layer. The hard coating layer includes particles modified to have reactivity and a binder resin, and the content of the particles is 1 part by weight or more and 60 parts by weight or less based on 100 parts by weight of the binder resin solid content.

In addition, the hard coat film of the present invention preferably has an average particle diameter of 100 nm or more and 1,000 nm or less.

In addition, in the hard coating film of the present invention, suitably, when the particles constitute secondary particles as an aggregate of primary particles, the diameter of the primary particles is 1 nm or more and 100 nm or less.

In addition, the hard coating film of the present invention is suitably one or a combination of two or more wherein the particles are selected from silica, alumina, titanium, zirconia, calcium carbonate, magnesium carbonate, barium sulfate.

In addition, in the hard coating film of the present invention, the particles suitably have one or a combination of two or more of functional groups selected from an acryloyl group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, and an isocyanate group.

Further, the hard coat film of the present invention preferably has a value of the flex resistance test of the hard coat layer measured by a cylindrical mandrel method in accordance with JIS-K5600-5-1 (1999) of 6 mm or less.

In addition, the hard coating film of the present invention suitably laminates an inorganic compound layer on the film and in an hourglass cross-cut peeling test after boiling, the inorganic compound layer is only partially peeled from the hard coating layer, or better than that.

Further, in the hard coat film of the present invention, the inorganic compound layer is preferably an optical adjustment layer or a gas barrier layer.

In addition, the hard coating film of the present invention is suitably the inorganic compound is SiO ₂ or Nb ₂ Ox (provided that 4≤x≤5).

In addition, the hard coating film of the present invention is suitably composed of a single layer or multiple layers of the inorganic compound layer.

In addition, the transparent conductive film of the present invention is characterized by using the hard coating film of the present invention described above.

In addition, the touch panel of the present invention is characterized by using the hard coating film of the present invention described above.

According to the present invention, it is possible to improve the adhesion between the inorganic compound layer and the hard coating layer. In particular, there is little change with the passage of time, and the adhesiveness is maintained well.

Figure 1 (a) is a cross-sectional view showing an example of an embodiment of the hard coat film of the present invention, (b) is a cross-sectional view showing another example of the embodiment of the hard coat film of the present invention, (c) is the present invention It is a cross-sectional view showing another example of the embodiment of the hard coat film.
2 is a cross-sectional view illustrating an example of a hard coating film on which an inorganic compound layer is laminated.
3 is a top view for explaining the shape of the cut in the hourglass cross-cut peeling test.
4 (a) is a cross-sectional view showing an example of a transparent conductive film to which the hard coating film of the present invention is applied, (b) is a cross-sectional structure of the transparent conductive film of (a) to which the transparent conductive film is etched and the transparent conductive film It is a diagram explaining the reflected light.
Figure 5 (a) is a cross-sectional view of the hard coating film of the present invention in which the SiO ₂ film is laminated on the hard coating layer, (b) is a Nb ₂ Ox (only 4≤x≤5) film and SiO ₂ film is hard in this order It is a cross-sectional view of the hard coating film of the present invention laminated on the coating layer.

An embodiment of the hard coating film 1 for adhering the inorganic compound layer 40 of the present invention will be described below with reference to FIGS. 1 to 5 . In addition, as long as the inorganic compound layer 40 is a layer containing an inorganic compound, the case of a layer containing an inorganic compound may be sufficient, and the case of the case of the layer of the inorganic compound itself may be sufficient as it.

The hard coating film 1 of the present invention has a hard coating layer 20, and includes particles (reactive modified particles) 21 and a binder resin 22 modified so that the hard coating layer 20 has reactivity, and a reactive formula It is characterized in that the content of the 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 this invention is provided with the hard-coat layer 20 formed on the support body 10 and the support body 10, as shown to Fig.1 (a) as a basic structure. The hard coating film 1 may be not only the one shown in FIG. 1 (a), but also a film of a single hard coating layer (FIG. 1 (b)), the surface opposite to the surface on which the hard coating layer 20 of the support 10 is formed The back coating layer (FIG. 1(c)) may be provided.

As shown in FIG. 2 , in the hard coating film 1 , the inorganic compound layer 40 is laminated on the hard coating layer 20 . In this case, the hard coating layer 20 has excellent adhesion to the inorganic compound layer 40 .

First, the reactive modifier particles 21 and the binder resin 22 constituting the hard coating layer 20 will be described.

The binder resin 22 has a function as a binder of the reactive modifying particles 21 to be described later. The binder resin 22 preferably has a reactive functional group. In this case, it is possible to effectively prevent the reactive modifier particles 21 from falling off by bonding with the reactive functional group of the reactive modifier particles 21 . Examples of the reactive functional group of the binder resin 22 include an acryloyl group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, and an isocyanate group.

As the binder resin 22, a resin such as an ionizing radiation curable resin, a thermosetting resin, or a thermoplastic resin may be used alone or in combination of two or more, and may be used separately depending on the purpose. Among them, when more excellent hardness is required, it is preferable to use an ionizing radiation curing resin.

Examples of the ionizing radiation curable resin include resins that can be crosslinked and cured by irradiation with ionizing radiation (ultraviolet rays or electron beams). For example, an acrylic resin having one or two or more (meth)acryloyl groups in one molecule is particularly It is preferably used. Examples of the acrylic compound include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, polyfluoroalkyl (meth) acrylate, silicone (meth) acrylate, etc. can be heard

Examples of the thermosetting resin include polyester acrylate-based resins, polyurethane acrylate-based resins, epoxy acrylate-based resins, epoxy-based resins, melamine-based resins, phenolic resins, and silicone-based resins.

Examples of the thermoplastic resin include polyester resins, acrylic resins, polycarbonate resins, cellulose resins, acetal resins, vinyl resins, polyethylene resins, polystyrene resins, polypropylene resins, polyamide resins, A polyimide-type resin, a fluorine-type resin, etc. are mentioned.

Moreover, it is more preferable that the binder resin 22 contains a fixed amount of high molecular weight resin. By combining the high molecular weight resin and the reactive modifier particles 21 to be described later, a certain degree of flexibility can be imparted to the hard coating layer 20 without impairing the hardness, and the inorganic compound layer 40 for the hard coating layer 20. The anchor of the 40 The effect increases. Accordingly, the adhesion between the hard coating layer 20 and the inorganic compound layer 40 is further improved.

High molecular weight resin is resin with a weight average molecular weight (Mw) of 10,000 or more, Preferably it is 10,000-150,000, More preferably, it is 30,000-100,000.

As the high molecular weight resin, a resin such as an ionizing radiation curable resin, a thermosetting resin, or a thermoplastic resin may be used alone or in combination of two or more. 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 of the binder resin 22 .

As content, it is 1 weight part or more and 50 weight part or less with respect to 100 weight part of binder resin 22 (solid content), More preferably, they are 5 weight part or more and 40 weight part or less. In addition, when the binder resin 22 contains high molecular weight resin, "binder resin 22 (solid content)" means the solid content of the binder resin 22 whole containing high molecular weight resin.

The reactive modifier particles 21 contribute to improving the adhesion of the hard coating 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 group is combined with the reactive functional group of the binder resin 22 to prevent the reactive modifier particles 21 from falling off from the hard coating layer 20 . Moreover, by having a reactive functional group, it is guessed that adhesiveness with an inorganic compound layer can be maintained even in a high-temperature and high-humidity state.

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. Examples of the reactive functional group include an acryloyl group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, and the like, and may be used alone or in combination of two or more of these reactive functional groups.

The content of the reactive modifying particles 21 is 1 part by weight or more with respect to 100 parts by weight of the binder resin 22 (solid content), the lower limit of the reactive modifying particles 21 in order to exhibit adhesion to the inorganic compound layer 40; Preferably it is 3 parts by weight or more, more preferably 5 parts by weight or more, and most preferably 10 parts by weight or more. On the other hand, the upper limit of the reactive modifying particles 21 is not particularly determined, but 60 parts by weight or less, preferably 40 parts by weight or less, more preferably 30 parts by weight or less based on 100 parts by weight of the binder resin 22 (solid content) to be.

When the content of the reactive modifier particles 21 is less than the above-described range, the adhesion to the inorganic compound layer 40 tends to be weak. On the other hand, when there is more than the above-mentioned range, it becomes difficult to maintain transparency, and it is unpreferable.

The reactive modifier particles 21 may be primary particles or secondary particles that are aggregates as long as they have a predetermined size. However, in order to obtain more adhesiveness, secondary particles are preferable. When secondary particles, which are aggregates of primary particles, are used as the reactive modified particles 21, it is not clear why the adhesion is improved compared to the case where primary particles of the same size are simply used, but the inorganic particles protruding on the surface It is considered that this is because the contact area with the compound layer 40 increases.

The average particle diameter of the reactive modifier particles 21 (including primary particles or secondary particles as aggregates made of primary particles) is different depending on the thickness of the hard coating layer 20, so it cannot be said uniformly, but the lower limit is It is 100 nm or more, Preferably it is 110 nm or more, More preferably, it is 130 nm or more. Moreover, an upper limit is 1,000 nm or less, Preferably it is 800 nm or less, More preferably, it is 600 nm or less. In addition, when the reactive modified particles 21 among the above are composed of secondary particles as an aggregate of primary particles, the lower limit of the average particle diameter of the primary particles constituting the secondary particles is 1 nm or more, preferably 20 nm or more , more preferably 30 nm or more. Moreover, an upper limit is 100 nm or less, Preferably it is 80 nm or less, More preferably, it is 60 nm or less.

When the average particle diameter of the reactive modifier particles 21 or the reactive modifier particles 21 is composed of secondary particles, the adhesiveness to the inorganic compound layer 40 can be obtained by setting the average particle diameter of the primary particles to the above-mentioned lower limit or more. have. On the other hand, by making these average particle diameters below the above-mentioned upper limit, respectively, the light transmittance which can be used for a transparent purpose can be acquired.

In addition, the average particle diameter of particle|grains points out the value of the volume average particle diameter (D50) which can be measured by the laser diffraction/scattering method.

The hard coating layer 20 may further contain a photoinitiator, a curing agent, and the like depending on the curing method.

Examples of the photoinitiator include photoradical polymerization initiators such as acetophenones, benzophenones, Michler ketone, benzoin, benzylmethyl ketal, benzoylbenzoate, α-acyloxime ester, and thioxanthone, onium salts, sulfonic acid esters, organic A photocationic polymerization initiator, such as a metal complex, is mentioned.

Moreover, as a hardening|curing agent, compounds, such as a polyisocyanate, an amino resin, an epoxy resin, and carboxylic acid, can be used suitably according to suitable resin.

In the hard coating layer 20, in addition to the binder resin, polymer resin, reactive modifier particles, photoinitiator, and curing agent, additives such as antistatic agent, dispersant, coagulant, UV absorber, antioxidant, and leveling agent are added within the range that does not impair performance. You may include additionally.

The thickness of the hard coating layer 20 (see L in Fig. 1 (a)) is 0.1 to 10.0 μm, preferably 0.5 to 5.0 μm, more preferably when the hard coating film 1 includes the support 10 . is 1.0-3.0 μm. In addition, when the hard coating film 1 is provided with a back coating layer 30 in addition to the support 10, 0.1 to 10.0 μm, preferably 1.0 to 5.0 μm, more preferably 1.0 to 3.0 μm. By having such a thickness, the adhesion between the hard coating layer 20 and the inorganic compound layer 40 is improved.

In addition, in the case of a single hard coat layer, the thickness is 0.1 to 10.0 μm, preferably 0.5 to 5.0 μm, more preferably 1.0 to 3.0 μm. When the thickness is 0.1 µm or more, the coating film strength is made sufficient while having adhesiveness with the inorganic compound layer 40, and the handling property is made good.

The thickness of the hard coating layer 20 is measured using a reflection spectroscopic film thickness meter (Otsuka Electronics FE-300).

Next, the support 10 when the hard coating film 1 has the support 10 will be described. The support 10 may be used without particular limitation as long as it is a plastic film having high optical transparency. For example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polycycloolefin, polyethylene, polycarbonate, polypropylene, polystyrene, triacetyl cellulose, acrylic, polyvinyl chloride, norbornene compound, etc. can be used A polyethylene terephthalate film subjected to double stretching, particularly biaxial stretching, is preferred in view of excellent mechanical strength and dimensional stability. In addition, in order to improve the adhesiveness with the hard coating layer 20, corona discharge treatment on the surface or one provided with an easy-to-adhesive layer is also suitably used. In addition, it is preferable that the thickness of the support body 10 is about 6-250 micrometers normally, More preferably, it is about 23-188 micrometers.

It is preferable that the support body 10 is light-transmissive, and specifically, it is 85% or more in total light transmittance (JISK7136), Preferably it is 90% or more.

In addition, as described above, the hard coating film 1 may further include a back coating layer 30 (FIG. 1 (c)) on the opposite side to the hard coating layer 20 of the support 10.

In this case, the back coating layer 30 is not particularly limited, but may be selected from a hard coating layer, an adhesive layer, an antistatic layer, and the like, and may also include the hard coating layer 20 described above.

The manufacturing method of the hard coat film 1 is not particularly limited, but, for example, when having the support 10, the above-described hard coat layer 20 material is dissolved or dispersed in a suitable solvent. It can be prepared by coating on a support by a known method such as coating, drying, and irradiating ultraviolet rays as needed. In addition, by forming a release layer (release layers) on the support 10 in advance, the hard coating layer 20 is formed on the support 10, and then the support 10 is peeled off and removed to form a single layer of the hard coating layer. can be done with In addition, in the case of the hard coating film 1 having the back coating layer 30 , the back coating layer dissolved or dispersed in a suitable solvent on the opposite side to the hard coating layer 20 of the support 10 having the hard coating layer 20 . It can be produced by applying the solvent coating solution by a known method such as bar coating, drying it, and irradiating ultraviolet rays if necessary.

Next, the characteristics of the hard coating layer 20 will be described. The properties to be provided by the hard coating layer 20 are adhesiveness and flexibility.

First, the adhesion is, for example, a state in which an inorganic compound layer is laminated and no treatment is performed (hereinafter referred to as "initial adhesion test") and a state after performing a boiling treatment, which is an accelerated weather resistance test (hereinafter, "adhesion after boiling"). "Property test") An hourglass cross-cut peeling test is performed in two types of conditions, and superiority or inferiority can be judged and evaluated according to the results. In the hourglass cross-cut peeling test, as described later, since the surface of the inorganic compound layer 40 is cross-cut in an hourglass-like shape to perform peeling, the adhesiveness is superior or inferior under harsher conditions than when cross-cut in a grid shape. can be evaluated.

Here, the initial adhesion test method (hourglass cross-cut peel test method) is as follows.

An inorganic compound (eg, SiO ₂ , Nb ₂ Ox (however, 4≤x≤5), etc.) is sputtered on the hard coating film 1 to prepare a test piece in which an inorganic compound layer 40 having a thickness of about 200 nm is formed into a film (Test specimen manufacturing process).

Next, as shown in FIG. 3 , the line segment DD' and the line segment EE' are parallel, and an incision is made in the surface of the inorganic compound layer 40 so that the width between these line segments is 2 cm. Next, the line segments FF' and GG' intersect each other, one end of the line segments FF' and GG' intersect the line segment DD', respectively, and the other end of the line segments FF' and GG' intersect the line segment EE', respectively. An incision is made on the surface of the inorganic compound layer 40 to do so. At this time, an incision is made so that the two triangles ABC and AB'C' formed by the line segments DD', EE', FF' and GG' become 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 of the line segment GG' on the line segment DD' and the line segment FF' is the point B and the point C, respectively, the line segment GG' on the line segment EE' and Let the intersection of the line segment FF' be a point B' and a point C', respectively (cutting process).

An adhesive tape (Cellotape (registered trademark) manufactured by Nichiban Corporation) is adhered as if covering two isosceles triangles with incisions, and the adhered adhesive tape is peeled off at a predetermined angle and speed (first peeling). Next, using the newly prepared adhesive tape on the test piece after the 1st peeling, the peeling test is similarly performed again at the same place where the 1st peeling was performed (2nd peeling). In addition, it is performed based on the cross-cut method prescribed|regulated to JISK5600-5-6 except the above-mentioned cutting method and performing peeling twice at the same place in succession (peeling process).

It is tested according to the initial adhesion test method, and in the present invention, the adhesion of the hard coating layer is preferably not peeled at all from the inorganic compound layer 40 from the hard coating layer 20 in the second peeling. By having such adhesiveness, the adhesiveness to the inorganic compound layer 40 over time is improved.

In the post-boiling adhesion test method, the test piece obtained in the test piece production step after the test piece production step in the initial adhesion test method described above and before the cutting step is boiled using pure water for a predetermined time. It is different from the initial adhesion test method in that it has a treatment process (boiling treatment process).

In addition, in the boiling treatment process, the inorganic compound layer 40 is SiO ₂ In this case, boil for 6 hours. In addition, when the inorganic compound layer 40 is Nb ₂ Ox (however, 4≤x≤5), it is boiled for 1 hour.

Tested according to the adhesion test method after boiling, in the present invention, the adhesiveness of the hard coating layer is that the inorganic compound layer 40 is only partially peeled from the hard coating layer 20 in the first or second peeling, or it is better than that Preferably, in the first or second peeling, it is more preferable that the inorganic compound layer 40 is only partially peeled from the hard coating layer 20, and in the second peeling, the inorganic compound layer 40 is the hard coating layer ( 20), it is more preferable that it does not peel at all.

By having such adhesiveness, the adhesiveness to the inorganic compound layer 40 in a high-temperature and high-humidity state is improved.

Or, when the initial adhesion test and the adhesion test method after boiling are combined, in the present invention, the adhesion of the hard coating layer 20 is the inorganic compound layer 40 from the hard coating layer 20 in the second peeling of the initial adhesion test. It is preferable that there is no peeling at all, and that the inorganic compound layer 40 is only partially peeled from the hard coating layer 20 in the first peeling of the adhesive test after boiling, and in the second peeling of the initial adhesive test It is better than that the inorganic compound layer 40 is not peeled off from the hard coating layer 20 at all, and that the inorganic compound layer 40 is only partially peeled from the hard coating layer 20 in the second peeling of the adhesion test after boiling more preferably.

By having such adhesiveness, it is difficult to change over time even in a harsh environment such as high temperature and high humidity, so that initial adhesiveness can be maintained.

In addition, the flexibility of the hard coating layer 20 can be evaluated by a flex resistance test. The value of the flex resistance test is different depending on the type or thickness of the material or thickness of the hard coating layer 20, or when the hard coating film 1 has the support 10 and the back coating layer 30, so this In the specification, a film thickness of 125 μm of an easily adhesive PET film “KFL10W” manufactured by Teijin DuPont Co., Ltd. was used as a support, and a flex resistance test was performed on the back side under conditions in which a layer other than an easily adhesive layer was not laminated.

In the present invention, the value of the flex resistance test (diameter of the iron bar at which cracks in the hard coating layer or peeling from the support first occurred) is preferably 6 mm or less, more preferably 2 mm or less. By setting the value of the flex resistance test to a predetermined value or less, the hard coating layer 20 has flexibility to improve adhesion to the inorganic compound layer 40 . 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 to be provided by the hard coating film (1) of the present invention will be described.

As an optical characteristic of the hard coat film 1, the total light transmittance (JISK7136) is preferably 85% or more, and more preferably 90% or more. By providing such light transmittance, it is possible to impart adhesion to the inorganic compound layer 40 without interfering with the visibility of a display device to which the hard coating 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. A suitable haze can be maintained by adjusting the content according to the average particle diameter of particle|grains.

Next, an application example of the hard coat film 1 will be described taking the hard coat film 1 of the structure shown in Fig. 1(a) as an example.

An example of the hard coating film (laminated body) 2 in which the inorganic compound layer 40 was laminated|stacked in FIG. 2 is shown. The laminate 2 is formed by bonding the inorganic compound layer 40 on the hard coating layer 20 of the hard coating film 1 to form a laminate.

As the inorganic compound layer 40 , the optical adjustment layer 50 or the gas barrier layer 51 is exemplified.

When the optical adjustment layer 50 is laminated on the hard coat layer 20, the hard coat film 1 is used for the film 3 with an optical adjustment layer (FIG. 2). In addition, as shown in Fig. 4(a), the transparent conductive film 60 is further laminated on the optical adjustment layer 50, so that the hard coat film 1 of this 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 an electrode sheet member of a capacitive type or resistive film type touch panel.

As an inorganic compound of the optical adjustment layer 50, what is necessary is just to adjust the optical characteristic of the transparent conductive film 60, SiO2, _Nb2Ox (however, _4≤x≤5 ), etc. are mentioned. In addition, the optical adjustment layer 50 may be comprised by a single layer or a multilayer. In the case of a single layer, as the optical adjustment layer 50, a SiO2 film|membrane is formed into _a film on the hard-coat layer 20 as shown to Fig.5 (a). In the case of a multilayer, as shown in FIG. 5(b) , for example, an Nb ₂ Ox (however, 4≤x≤5) film and a SiO ₂ film are laminated on the hard coat layer 20 in this order. Lamination of SiO ₂ or Nb ₂ Ox (however, 4≤x≤5) may be performed by a conventionally known method, and a film is formed by a sputtering method or a vapor deposition method.

Examples of the transparent conductive film 60 include a film made of tin-doped indium oxide (ITO), zinc oxide (ZnO), aluminum-doped zinc oxide (AZO), silver, copper or an alloy of copper, carbon nanotubes, or the like. The transparent conductive film 60 may be laminated by a conventionally known method, and is formed by a sputtering method such as DC sputtering or RF sputtering or a vapor deposition method. When used for a capacitive touch panel, a target electrode pattern is formed by etching the formed transparent conductive film 60 (FIG. 4(b)).

When such an electrode pattern is formed, the optical adjustment layer 50 makes 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 is the light 71 reflected from the ITO removal portion and the remaining portion of the ITO. The difference in optical characteristics (reflectance, color, transmittance, etc.) of the reflected light 70 is reduced to make it difficult to see the ITO electrode pattern.

On the other hand, when the gas barrier layer 51 is laminated on the hard coating layer 20, the hard coating film 1 is used as a gas barrier film 5 suitable for EL displays, EL lighting, solar cells, etc. (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 thereof. Aluminum or aluminum oxide is preferably used in view of workability and cost. Lamination of the gas barrier layer 51 on the hard coat layer 20 may be performed by a conventionally known method, and is formed by a sputtering method or a vapor deposition method.

According to the hard coating film (1) of the present invention, it is possible to improve the adhesion of the hard coating layer (20) to the inorganic compound layer (40). In particular, it is possible to maintain good adhesion properties with little change over time.

Example

Examples of the protective film of the present invention will be described below. In addition, in the examples below, "%" and "parts" are all based on weight, unless otherwise specified.

<Example 1>

Apply the following formulation for hard coating on one side of a 125 μm thick polyethylene terephthalate film (KFL10W manufactured by Teijin DuPont), dry, irradiate with UV light and harden to form a 2.0 μm thick hard coat layer. The hard coating film of Example 1 was prepared.

<Coating solution for hard coating>

・Binder resin

30 parts of ionizing radiation curable resin

(Unidic 17-813: DIC company, solid content 80%)

15 parts of high molecular weight resin

(Acrylic Dick A195: DIC Corporation, solid content 40%)

(A weight average molecular weight: 85,000)

15 parts of reactive modified particle dispersion

(SIRMIBK 30 WT%-M06: CIK Nanotech, solid content 30%)

(Silica particles: average primary particle diameter of 30 nm, average secondary particle diameter of 200-300 nm)

・60 parts of diluent solvent

· Photoinitiator 0.4 parts

(Irgacure 184: BASF)

<Example 2>

A protective film of Example 2 was obtained in the same manner as in Example 1 except that the weight part of the reactive modifier particles in the coating solution for hard coating of Example 1 was changed to 30.

<Example 3>

A protective film of Example 3 was obtained in the same manner as in Example 1 except that the weight part of the reactive modifier particles in the coating solution for hard coating of Example 1 was changed to 60.

<Comparative Example 1>

A protective film of Comparative Example 1 was obtained in the same manner as in Example 1, except that reactive modifier particles were excluded from the coating solution for hard coating of Example 1.

The following properties were evaluated for the protective films prepared in Examples and Comparative Examples described above.

1. Optical Characteristics

According to the JISK7136 measurement method, the total light transmittance (Tt) and haze ( Haze) was measured.

2. Regarding "bending resistance", based on the bending resistance (cylindrical mandrel method) in accordance with JIS-K5600-5-1 (1999), prepare iron rods with diameters of about 3 mm and 7 mm, and use each iron rod to harden it. Each of the protective film with a coating layer is folded and wound so that the hard coating layer 20 is on the outside, and whether the hard coating layer 20 of the wound part is cracked or peeled from the support is visually observed. As a result, “○” indicates that no cracking or peeling from the support was confirmed in the 3 mm iron bar, and cracking or peeling from the support was confirmed in the 3 mm iron bar, but cracking or peeling from the support was observed in the 7 mm iron bar. Those that were not confirmed were evaluated as "Δ", and those in which cracks or peeling from the support were confirmed in all the iron bars were evaluated as "x".

3. Initial adhesion test (hourglass cross-cut peel test)

SiO ₂ or Nb ₂ Ox (however, 4≤x≤5) was sputtered with a sputtering device (manufactured by Shibaura Mechatronics: CFS-4EP-LL) on the hard coating layer of the hard coating film prepared in the above Examples and Comparative Examples. , a test piece on which an inorganic compound layer 40 having a thickness of about 200 nm was formed was prepared (test piece preparation step).

Next, as shown in FIG. 3 , the line segment DD' and the line segment EE' were parallel, and a cut was made in the surface of the inorganic compound layer 40 so that the width between these line segments was 2 cm. Next, the line segments FF' and GG' intersect each other, one end of the line segments FF' and GG' intersect the line segment DD', respectively, and the other end of the line segments FF' and GG' intersect the line segment EE', respectively. An incision was made on the surface of the inorganic compound layer 40 to do so. At this time, an incision was made so that the two triangles ABC and AB'C' formed by the line segments DD', EE', FF' and GG' became 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 of the line segment GG' on the line segment DD' and the line segment FF' is the point B and the point C, respectively, and the line segment GG' on the line segment EE' and The points of intersection of the line segments FF' were set as points B' and C', respectively (cutting process).

An adhesive tape (Cellotape (registered trademark) manufactured by Nichiban Corporation) was adhered as if covering two isosceles triangles with incisions, and the adhered adhesive tape was peeled off at a predetermined angle and speed (first peeling). Next, using the newly prepared adhesive tape for the test piece after the 1st peeling, the peeling test was similarly done again at the same place where the 1st peeling was performed (2nd peeling). In addition, it is performed based on the cross-cut method prescribed|regulated to JISK5600-5-6 except the above-mentioned cutting method and performing peeling twice at the same place in succession (peeling process).

In this peeling test, when the inorganic compound layer 40 was not peeled off from the hard coating layer 20 at all, ○ (no peeling), and the inorganic compound layer 40 was partially peeled from the hard coating layer 20, △ (partial peeling) Existing), the inorganic compound layer 40 was almost completely peeled off from the hard coat layer 20 was evaluated as × (all peeled).

4. Adhesion test method after boiling

When the inorganic compound layer is SiO ₂ , the test piece was boiled in pure water for 6 hours after the test piece preparation process of the initial adhesion test described above (boiling treatment process). Then, the above-described cutting process and peeling process were performed to ensure that the inorganic compound layer 40 was not peeled off from the hard coating layer 20 at all (no peeling), and the inorganic compound layer 40 was partially peeled from the hard coating layer 20 What exists was made into (triangle|delta) (there is partial peeling) and the thing in which the inorganic compound layer 40 has peeled from the hard-coat layer 20 almost entirely was made into * (total peeling).

When the inorganic compound layer is Nb ₂ Ox (however, 4≤x≤5), tests and evaluations are performed in the same manner as in the case of SiO ₂ described above, except that the boiling time is 1 hour in the above-described boiling treatment process. did.

Table 1 shows the results.

Regarding the adhesive evaluation, in the films of Examples 1 to 3, the adhesion to SiO ₂ and Nb ₂ Ox (however, 4≤x≤5) of the initial adhesion test was “peelable” in both the first and second peeling None” was. In addition, the adhesion to SiO ₂ of the adhesion test after boiling of these examples is "no peeling" in the first peeling, "partial peeling" or "no peeling" in the second peeling, Nb ₂ Ox (however, 4≤ The adhesiveness with respect to x≤5) was "no peeling" in both peeling of the 1st time and 2nd time except Example 1.

On the other hand, the evaluation of adhesion to SiO ₂ and Nb ₂ Ox (however, 4≤x≤5) of the film of Comparative Example 1 was inferior to that of Examples 1 to 3 in the initial adhesion test, and the adhesion test after boiling In , it was "all peeling".

These results show that the films of Examples 1 to 3 having the reactive modifier particles 21 are difficult to change over time even in a harsh environment such as high temperature and high humidity, so that the adhesion to the initial inorganic compound layer 40 can be maintained. showed that

Regarding the flexibility, Examples 1 to 3 had more flexibility than Comparative Example 1. Therefore, it was found that the adhesion to the inorganic compound layer 40 was improved by providing the hard coating layer 20 with adequate flexibility.

1... Hard coating film, 2... Laminate, 3... Film with optical adjustment layer, 4... Transparent conductive film, 5... Gas barrier film, 20... Hard coat layer, 21... ··Reactive modified particles, 22···Binder resin, 40···Inorganic compound layer, 50···Optical adjustment layer, 51···Gas barrier layer, 60···Transparent conductive film, 70··Light, 71 ···light

Claims (12)

As a hard coating film having a hard coating layer for adhering an inorganic compound layer,
The hard coating layer includes particles modified to have reactivity, and a binder resin having a reactive functional group binding to the reactive functional group of the particle,
The content of the particles is 1 part by weight or more and 60 parts by weight or less based on 100 parts by weight of the binder resin solid content,
The average particle diameter of the particles is 100 nm or more and 1,000 nm or less,
When the particles constitute secondary particles as an aggregate of primary particles, the diameter of the primary particles is 1 nm or more and 100 nm or less,
Hard coating film, characterized in that the thickness of the hard coating layer is 0.1 ~ 10.0 ㎛. As the hard coating film according to claim 1,
The hard coating film, characterized in that the particles are one or a combination of two or more selected from silica, alumina, titanium, zirconia, calcium carbonate, magnesium carbonate, barium sulfate. As the hard coating film according to claim 1,
The hard coating film, characterized in that the particles have one or a combination of two or more of a functional group selected from an acryloyl group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, and an isocyanate group. As the hard coating film according to claim 1,
A hard coating film, characterized in that the value of the flex resistance test of the hard coating layer measured by the cylindrical mandrel method in accordance with JIS-K5600-5-1 (1999) is 6 mm or less. As the hard coating film according to claim 1,
In an hourglass cross-cut peeling test after laminating an inorganic compound layer on the film and boiling, the inorganic compound layer is only partially peeled off from the hard coating layer or is better than that. As the hard coating film according to claim 1,
The hard coating film, characterized in that the inorganic compound layer is an optical adjustment layer or a gas barrier layer. As the hard coating film according to claim 1,
The inorganic compound is a hard coating film, characterized in that SiO ₂ or Nb ₂ Ox (provided that 4≤x≤5). As the hard coating film according to claim 1,
Hard coating film, characterized in that 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 8. A touch panel using the hard coat film according to any one of claims 1 to 8. delete delete

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