TWI631012B - Transparent conductive film having protection film - Google Patents

Abstract

The present invention provides a transparent conductive film with a protective film which is excellent in operability and can effectively suppress the occurrence of curl even when an annealing process is performed.

This transparent conductive film is a transparent conductive film with a protective film formed by laminating a transparent conductive film, a first hard coating layer, a transparent plastic film substrate, a second hard coating layer, and a protective film from above. The film is composed of an adhesive layer and a protective film substrate, and is peelably laminated on the second hard coat layer. The transparent plastic film substrate has a heat shrinkage rate of 0.6% or less in the MD direction when heated at 150 ° C for 60 minutes. The thermal shrinkage rate of the protective film substrate in the MD direction when heated at 150 ° C. for 60 minutes is a value of 0.6% or less.

Description

Transparent conductive film with protective film

The present invention relates to a transparent conductive film with a protective film.

In particular, it is a transparent conductive film with a protective film which is excellent in operability and can effectively suppress the occurrence of curl even when an annealing process is performed.

Conventionally, a touch panel capable of inputting information by directly contacting an image display unit is configured by disposing a light-transmissive input device on a display.

As a representative form of the above-mentioned touch panel, there are a resistive film type touch panel in which two transparent electrode substrates are arranged with a gap so that the respective transparent electrode layers face each other, and use is made between a transparent electrode film and a finger. Capacitive touch panel with changes in electrostatic capacitance.

Among them, in a capacitive touch panel, as a thin film sensor for detecting a touch position of a finger, a transparent conductive film in which a transparent conductive film is laminated on a transparent plastic film substrate is widely used.

In addition, in order to increase the conductivity of the transparent conductive film in the transparent conductive film, a so-called annealing treatment is widely performed, that is, by This transparent conductive film in a state of being laminated on a transparent plastic film is subjected to a heat treatment to crystallize it.

In addition, along with the demand for thinning of a smart phone or the like equipped with an electrostatic capacitance type touch panel, a thinning of a transparent conductive film is also required.

On the other hand, a transparent conductive film requires high durability due to the use of a touch panel, and also requires precise dimensional stability from the viewpoint of precisely forming a patterned transparent conductive film.

Therefore, in order to respond to these demands, a hard-coated film having a hard-coat layer on the surface of a transparent plastic film substrate is disclosed (for example, refer to Patent Document 1).

That is, Patent Document 1 discloses a hard-coated film, which is characterized in that a hard-coated film having a hard-coat layer on one side of a plastic substrate film (transparent plastic film substrate) and satisfies the following conditions (1) to (5).

(1) The thickness of the plastic substrate film is 50μm ~ 500μm

(2) The film thickness of the hard coat layer is 1 μm to 30 μm

(3) The pencil hardness of the hard coating film is H or higher

(4) Heat shrinkage after treatment at 150 ° C for 30 minutes is 0.1% to 2% or less

(5) The crimp value measured at 150 ° C for 30 minutes using the following measurement method is 0 mm to 5 mm

(test methods)

Cut the hard-coated film into 20 cm in length, 2 cm in width, and 2 cm in length and 20 cm in width. In the sample, it was left in a hot-air loop-type oven at 150 ° C for 30 minutes to perform heat treatment. After being left to cool at room temperature, the plastic substrate film was placed face down on the glass plate, and the floating amount of the glass plate surface at four angular distances in the vertical direction was measured. In the two film samples cut out, the maximum floating amount was taken as the curl value.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Laid-Open No. 2011-31457 (Scope of patent application)

However, it has been found that the hard-coated film disclosed in Patent Document 1 has a feature of having a hard-coat layer only on one side of a transparent plastic film substrate. Therefore, it is difficult to reliably suppress Curling occurs due to the difference between the thermal shrinkage rate and the thermal shrinkage rate of the transparent plastic film substrate.

In addition, in order to compensate for the decrease in operability due to the reduction in thickness, in recent transparent conductive films, a method has been adopted in which a surface of a transparent plastic film substrate that is opposite to the side on which the transparent conductive film is formed is A protective film that can be peeled off is laminated auxiliaryly, and finally peeled off.

In this regard, it has been found that, in the hard-coated film disclosed in Patent Document 1, even if it is a hard-coated film alone, the occurrence of curl can be suppressed to some extent, but in a state where the protective film is laminated, The difference between the thermal shrinkage of the hard-coated film and the thermal shrinkage of the protective film causes significant curling.

Therefore, in view of the above situation, the inventors have made unremitting efforts and found that by providing hard coatings on both sides of the transparent plastic film substrate, In addition, the thermal shrinkage ratios of the transparent plastic film substrate and the protective film substrate under the specified conditions in the MD direction were each within a predetermined range, so that even when annealing was performed, the occurrence of curling could be effectively suppressed, and the present invention was completed. invention.

That is, an object of the present invention is to provide a transparent conductive film with a protective film which is excellent in operability and can effectively suppress the occurrence of curl even when an annealing process is performed.

According to the present invention, a transparent conductive film with a protective film can be provided to solve the above-mentioned problems, and is characterized in that a transparent conductive film, a first hard coating layer, a transparent plastic film substrate, a second hard coating layer and A transparent conductive film with a protective film made of a protective film. The protective film is composed of an adhesive layer and a protective film substrate and is releasably laminated on the second hard coat layer. The transparent plastic film substrate is heated at 150 ° C. The heat shrinkage rate in the MD direction at 60 minutes is 0.6% or less, and the heat shrinkage rate in the MD direction of the protective film substrate when heated at 150 ° C. for 60 minutes is 0.6% or less.

That is, if it is a transparent conductive film with a protective film of this invention, since it is supported by a protective film, it can provide excellent handleability to a thin transparent conductive film.

In addition, in the case of the transparent conductive film with a protective film of the present invention, the hard plastic layers are provided on both sides of the transparent plastic film substrate, and the MD of the transparent plastic film substrate and the protective film substrate under predetermined conditions are set Since the thermal shrinkage ratios in the directions are each within a predetermined range, the occurrence of curl can be effectively suppressed even when the annealing treatment is performed.

In addition, in the case of the transparent conductive film with a protective film of the present invention, since the hard coat layers are provided on both sides of the transparent plastic film substrate, curling of the transparent conductive film monomer after peeling the protective film occurs. Can also be effectively suppressed.

In addition, MD direction means the long side direction at the time of film formation, and TD direction means the width direction at the time of film formation.

In addition, the transparent conductive film with a protective film of the present invention refers to both the transparent conductive film with a protective film before and after the annealing treatment.

In addition, when constituting the transparent conductive film with a protective film of the present invention, the thermal shrinkage of the transparent plastic film substrate when heated at 150 ° C for 60 minutes and the protective film substrate at 150 ° C are preferred. The difference in the heat shrinkage rate in the MD direction when heated for 60 minutes is a value in the range of -0.5 to 0.5%.

With such a configuration, even when an annealing process is performed, the occurrence of curl can be more effectively suppressed.

In addition, when constituting the transparent conductive film with a protective film of the present invention, it is preferable that the thermal shrinkage ratio of the transparent plastic film base material in the TD direction when heated at 150 ° C. for 60 minutes is 0.6% or less, and the protective film The thermal shrinkage rate of the base material in the TD direction when heated at 150 ° C. for 60 minutes was a value of 0.6% or less.

With this configuration, even when the annealing process is performed, the occurrence of curl can be further effectively suppressed.

In addition, in the transparent guide with a protective film constituting the present invention, In the case of an electrical film, a transparent conductive film with a protective film is cut out into a square of 100 mm in the MD direction and 100 mm in the TD direction, and the protective film side is lowered and heated at 150 ° C for 60 minutes. The absolute value of the curl value at this time is preferable The value is 25 mm or less.

With this configuration, even when the annealing process is performed, the occurrence of curl can be further effectively suppressed.

In the case where the transparent conductive film with a protective film according to the present invention is configured, it is preferable that either the first hard coat layer and the second hard coat layer are made of a cured product of an active energy ray-curable resin composition. The weight ratio of the polymerizable compound (A) to the polymerizable compound (B) in the active energy ray-curable resin composition (polymerizable compound (A) / polymerizable compound (B)) is 15/85 to 85/15. The polymerizable compound (A) has two or more groups represented by the following general formula (1) in one molecule and does not contain an alkylene group in a structure other than the group. An oxygen unit, and the polymerizable compound (B) has three or more groups represented by the following general formula (2) in one molecule.

(In the general formula (1), R is an independent hydrogen atom or a methyl group, and * represents a bonding portion.)

(In the general formula (2), R ¹ is an independent hydrogen atom or a methyl group, A is an independent alkylene group having 1 to 5 carbon atoms, the repeating number n is an independent integer of 1 or more, and * represents a bond section.)

With this structure, it is possible to impart an appropriate surface hardness to the obtained hard coat layer and to disperse it. Alleviates deformation caused by heat shrinkage.

In addition, when the transparent conductive film with a protective film of the present invention is configured, the thickness of the first hard coat layer and the second hard coat layer is preferably a value in a range of 1 to 15 μm.

With this configuration, it is possible to suppress the occurrence of curling due to thermal shrinkage of the transparent plastic film substrate, and also to suppress generation of outgassing during the annealing treatment due to the hard coat layer.

In addition, when constituting the transparent conductive film with a protective film of the present invention, the thickness of the protective film substrate is preferably a value in the range of 10 to 300 μm.

With this structure, it is possible to suppress the occurrence of curling of the transparent conductive film during the annealing treatment, and also to suppress curling of the protective film substrate itself.

In addition, when constituting the transparent conductive film with a protective film of the present invention, the thickness of the transparent plastic film substrate is preferably a value in the range of 10 to 200 μm.

With such a configuration, it is possible to improve the uniformity of the thickness of the hard coat layer and the transparent conductive film, etc., and to suppress the generation of exhaust gas caused by the transparent plastic film substrate.

Moreover, when forming the transparent conductive film with a protective film of this invention, it is preferable to have an optical adjustment layer between a 1st hard-coat layer and a transparent conductive film.

With such a configuration, when the transparent conductive film is formed into a pattern shape by the etching process, it can be adjusted so that there is no difference in visibility between the existing portion and the non-existing portion of the transparent conductive film (the pattern shape is not visible).

1‧‧‧ transparent conductive film

10‧‧‧ transparent conductive film

2a‧‧‧1st hard coating

2b‧‧‧ 2nd hard coating

3‧‧‧ transparent plastic film substrate

4‧‧‧ Adhesive layer

5‧‧‧ Protective film substrate

6‧‧‧ transparent conductive film

7‧‧‧ protective film

8‧‧‧Optical adjustment layer

8a‧‧‧High refractive index layer

8b‧‧‧Low refractive index layer

1a to 1b are diagrams provided to explain the transparent conductive film with a protective film of the present invention.

FIG. 2 is a graph provided to explain the relationship between the thermal shrinkage of the transparent plastic film substrate in the MD direction and the curl value of the transparent conductive film with a protective film.

FIG. 3 is a graph provided to explain the relationship between the thermal shrinkage of the protective film substrate in the MD direction and the curl value of the transparent conductive film with the protective film.

FIG. 4 is a graph provided to explain the relationship between the difference in thermal shrinkage of the transparent plastic film substrate and the protective film substrate in the MD direction and the curl value of the transparent conductive film with the protective film.

As shown in FIG. 1a, the first embodiment of the present invention is a transparent conductive film with a protective film, which is characterized in that a transparent conductive film 1, a first hard coat layer 2a, and a transparent plastic film substrate 3 are laminated in this order. A transparent conductive film 10 with a protective film formed by the second hard coat layer 2b and the protective film 7. The protective film 7 is composed of an adhesive layer 4 and a protective film substrate 5, and is laminated on the second hard layer so as to be peelable. Coating 2b, thin transparent plastic The film substrate 3 has a heat shrinkage rate in the MD direction when heated at 150 ° C. for 60 minutes, and the protective film substrate 5 has a heat shrinkage rate in the MD direction when heated at 150 ° C. for 60 minutes. Value.

Hereinafter, embodiments of the present invention will be specifically described with reference to the drawings as appropriate.

1. Transparent plastic film substrate

(1) Type

The resin used as the transparent plastic film substrate is not particularly limited as long as it is excellent in flexibility and transparency, and examples thereof include polyethylene terephthalate (PET), polybutylene terephthalate, and poly Polyester film such as ethylene naphthalate, polycarbonate film, polyethylene film, polypropylene film, cellophane, diethyl cellulose film, triethyl cellulose film, cellulose acetate butyrate film, polyvinyl chloride Ethylene film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polymethylpentene film, polyfluorene film, polyetheretherketone film, polyetherfluorene film, Polyetherimide film, polyimide film, fluororesin film, polyimide film, acrylic resin film, polyurethane resin film, norbornene resin film, cycloolefin resin film and other plastic films.

Among them, a transparent resin film composed of polyethylene terephthalate or polycarbonate is preferably used from the viewpoint of excellent transparency and versatility.

(2) Thermal shrinkage

In the present invention, the transparent plastic film substrate has a heat shrinkage rate of 0.6% or less in the MD direction when heated at 150 ° C for 60 minutes. value.

The reason is that in combination with predetermined heat shrinkage characteristics of a protective film substrate described later, the occurrence of curl can be effectively suppressed even when the annealing treatment is performed in the state of the transparent conductive film with the protective film.

That is, if the thermal shrinkage ratio of the transparent plastic film substrate in the MD direction is greater than 0.6%, it may be difficult to effectively suppress the occurrence of curl regardless of the difference between the thermal shrinkage ratio of the transparent film substrate and the protective film substrate in the MD direction. . On the other hand, the lower limit value of the thermal shrinkage rate of the transparent plastic film substrate in the MD direction includes 0%. However, in order to make this lower limit value too small, it is necessary to add fine particles or the like or to mix materials having excellent heat resistance to deteriorate the optical characteristics.

Therefore, it is more preferable that the thermal shrinkage ratio of the transparent plastic film substrate in the MD direction when heated at 150 ° C. for 60 minutes is in the range of 0.01 to 0.5%, and more preferably in the range of 0.05 to 0.3%.

It should be noted that the interaction between the predetermined heat shrinkage characteristics of the transparent plastic film base material and the predetermined heat shrinkage characteristics of the protective film base material is achieved by shifting the two film base materials in the MD direction of the transparent plastic film base material. It adhere | attached so that it may correspond to the MD direction of a protective film base material.

In addition, in order to make the thermal shrinkage ratio of the transparent plastic film base material in the above range, it is basically easiest to select such a transparent plastic film base material, but heat-fixing treatment is performed at a predetermined temperature after biaxial stretching, and At this time, the relaxation direction in the MD direction can also be adjusted to adjust the heat shrinkage rate (for the heat shrinkage rate in the TD direction described later and the heat shrinkage in the protective film substrate). Shrinkage rate is the same).

Here, the relationship between the thermal shrinkage of the transparent plastic film substrate in the MD direction and the curl value of the transparent conductive film with a protective film will be described using FIG. 2.

That is, FIG. 2 shows the curl value of the transparent conductive film with a protective film with the thermal shrinkage (%) in the MD direction when the transparent plastic film substrate is heated at 150 ° C. for 60 minutes as the horizontal axis ( mm) is a scatter plot of the vertical axis.

In addition, the curl value of the transparent conductive film with a protective film is a value measured as follows.

That is, a transparent conductive film with a protective film was cut out into a square of 100 mm in the MD direction and 100 mm in the TD direction as a test piece, and the test piece was placed in a furnace at a temperature of 150 ° C. with the protective film side as the lower side. Leave for 60 minutes.

Next, the test piece was left to stand on a glass plate in an environment of a temperature of 23 ° C. and a humidity of 50% RH with the protective film side as a lower side for 60 minutes.

Then, the floating amount of the four angular distance glass plate surfaces of the test piece in the vertical direction was measured with a vernier caliper, and the largest value among the obtained floating amounts was taken as the curl value.

It should be noted that when the four corners do not float from the glass plate surface and the central part of the film floats, the front and back of the transparent conductive film with the protective film are flipped, and the float amount of the four corners is measured, and the float is lifted. The maximum value of the amount is marked with a negative sign as the curl value.

In addition, a transparent guide with a protective film as a measurement target As the electrical film, transparent conductive films prepared as Examples 1 to 5 and Comparative Example 1 described later were used.

That is, a transparent conductive film with a protective film such that the thermal shrinkage of the protective film substrate in the MD direction is 0.6% or less is used as a measurement target.

From the scatter diagram, it can be understood that if the thermal shrinkage of the protective film substrate in the MD direction is 0.6% or less, if the transparent plastic film substrate has a thermal shrinkage in the MD direction of 0.6% or less, The curl value can be controlled within a substantially allowable range of about -20 to 20 mm.

On the other hand, even if the thermal shrinkage ratio of the protective film substrate in the MD direction is 0.6% or less, it can be seen that if the thermal shrinkage ratio of the transparent plastic film substrate in the MD direction is more than 0.6%, curling occurs When the value becomes a value smaller than -40 mm or larger than 40 mm, it cannot be controlled within a substantially allowable range, which causes a problem.

Therefore, it can be understood from the scatter diagram shown in FIG. 2 that from the viewpoint of effectively suppressing the occurrence of curling of the transparent conductive film with a protective film, the thermal shrinkage of the protective film substrate in the MD direction is 0.6% or less. Under the condition of the value, the thermal shrinkage of the transparent plastic film substrate in the MD direction needs to be a value of 0.6% or less.

In addition, the thermal shrinkage rate of the transparent plastic film substrate in the TD direction when heated at 150 ° C. for 60 minutes is preferably a value of 0.6% or less.

The reason is that the thermal shrinkage of the transparent plastic film substrate in the TD direction is a value within the above range, so that even when the annealing process is performed, It is also possible to further effectively suppress the occurrence of curl.

That is, if the thermal shrinkage rate in the TD direction is greater than 0.6%, it may be difficult to effectively suppress the occurrence of curl regardless of the difference from the thermal shrinkage rate in the TD direction of the protective film substrate.

Therefore, it is more preferable that the thermal shrinkage rate of the transparent plastic film substrate in the TD direction when heated at 150 ° C. for 60 minutes is 0.5% or less, and more preferably 0.3% or less.

(3) Thickness

The thickness of the transparent plastic film substrate is preferably a value in a range of 10 to 200 μm.

The reason is that by setting the thickness of the transparent plastic film substrate to a value within the above-mentioned range, it is possible to improve the coatability of the hard coat layer and the subsequent lamination of the transparent conductive film and to suppress the formation of the transparent plastic film substrate The generation of exhaust.

That is, if the thickness of the transparent plastic film base material is less than 10 μm, thickness unevenness may occur during the lamination of the hard coat layer and the transparent conductive film. On the other hand, if the thickness of the transparent plastic film substrate is a value greater than 200 μm, generation of exhaust gas during annealing may be a problem.

Therefore, the thickness of the transparent plastic film substrate is more preferably a value in a range of 30 to 150 μm, and more preferably a value in a range of 50 to 100 μm.

2. Hard coating

In the present invention, it is characterized in that A first hard coat layer is provided on one side, and a second hard coat layer is provided on the other side.

These first hard coat layers and second hard coat layers may be made of different materials and may have different thicknesses, but from the viewpoint of effectively suppressing curling of the transparent conductive film monomer after peeling off the protective film, Preferably, they are made of the same material and have the same thickness.

Therefore, the first hard coat layer and the second hard coat layer will be described below without distinction.

(1) Material substance

The hard coat layer according to the present embodiment is a layer containing a cured product of an active energy ray-curable resin. The content of the cured product of the active energy ray-curable resin in this layer is preferably 70 to 100% by weight, more preferably 80 to 100% by weight, and still more preferably 90 to 100% by weight relative to the total weight of the hard coat layer. .

As this active energy ray curable resin (hereinafter, sometimes simply referred to as a curable resin), an active energy ray curable resin that can be used for a conventional hard coat layer can be freely used. In addition, from the viewpoint of maximizing the effect of suppressing curling occurring during the annealing treatment, the curable resin preferably contains a polymerizable compound (A), a polymerizable compound (B), and a photopolymerization initiator (C). Among them, The polymerizable compound (A) has two or more groups represented by the general formula (1) in one molecule and does not contain an alkylene oxide unit in a structure other than the group, and the polymerizable compound ( B) There are three or more groups represented by the general formula (2) in one molecule.

(i) Polymerizable compound (A) (hereinafter, sometimes referred to as (A) component)

The curable resin preferably contains a polymerizable compound (A). The synthetic compound (A) has two or more groups represented by the following general formula (1) in one molecule and does not contain an alkylene oxide unit in the structure other than the group. By containing a polymerizable compound (A), the surface hardness of the obtained hard-coat layer can be improved.

In the general formula (1), R is an independent hydrogen atom or a methyl group, and * represents a bonding portion.

The number of the groups represented by the general formula (1) contained in one molecule of the polymerizable compound (A) is two or more, preferably 2 to 16, more preferably 2 to 12, and even more preferably 3 ~ 10, more preferably 3 ~ 8.

If the number of the groups is less than 2, a sufficient cross-linked structure cannot be formed, and the surface hardness of the obtained hard coating layer is reduced. Therefore, the supporting function of the transparent plastic film substrate performed by the hard coating layer may not be sufficient. The occurrence of curl due to thermal shrinkage of the transparent plastic film substrate during the annealing process cannot be suppressed. On the other hand, if it is more than 16, the crosslinking density may become too high, and the softness of the obtained hard coat layer may be lost, and the deformation generated during the annealing treatment may not be dispersed. Ease, curling due to slight differences in hard coating on both sides, etc.

The polymerizable compound (A) is a compound that does not contain an alkylene oxide unit in the structure other than the group represented by the general formula (1). It is considered that the compound containing an alkylene oxide unit has a chain having a long alkylene oxide structure, so that the distance between crosslinking points becomes longer, and the overall structure of the obtained hard coating layer tends to become sparse. As a result, the surface hardness of the hard coating layer becomes Reason for reduction. Therefore, in the present invention, it is considered to improve the surface hardness of the obtained hard coat layer by using such a polymerizable compound as the (A) component.

Examples of such a polymerizable compound (A) include trimethylolpropane tri (meth) acrylate, bis (trimethylolpropane) tetra (meth) acrylate, and pentaerythritol tri (meth) acrylic acid. Ester, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol tri (meth) acrylate, ethylene glycol di (meth) acrylate , 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol A di (meth) acrylate and an oligoester (methyl group having two or more groups represented by the above-mentioned general formula (1) in the molecule and containing no alkylene oxide unit in the structure other than the group ) Acrylates, oligoether (meth) acrylates, oligourethane (meth) acrylates, and oligoepoxy (meth) acrylates.

In addition, these (A) components can be used individually or in combination of 2 or more types.

(ii) Polymerizable compound (B) (hereinafter, sometimes referred to as (B) component.)

The curable resin used in the present invention preferably contains a polymerizable compound (B) having three or more groups represented by the following general formula (2) in one molecule.

Polymerizable compounds (B) and (A) containing one or more (meth) acrylfluorenyl groups represented by the general formula (2) and one alkylene oxide chain directly bonded together in one molecule Component, and the resulting hard coat layer can have both the rigid portion due to the component (A) and the flexible portion due to the component (B). The rigid part can suppress the thermal shrinkage of the transparent plastic film substrate, and the soft part can reduce the deformation caused by the thermal shrinkage. It is considered that it can effectively suppress curl of the transparent conductive film by an annealing process from this.

In addition, the component (B) also has the effect of imparting an appropriate polarity to the surface of the hard coat layer. That is, even when the hard coat layer having the component (A) and the component (B) is formed into a nano-level coating film such as an optical adjustment layer described later, a depression of the coating liquid or the like is not generated, thereby preventing the optical adjustment layer. Defective.

In the general formula (2), R ¹ independently represents a hydrogen atom or a methyl group. In addition, * indicates a bonding part. A independently represents an alkylene group having 1 to 5 carbon atoms, preferably ethylene or propylene, and more preferably ethylene. By using A as the alkylene group, the obtained hard coating layer can have moderate flexibility, and the deformation of the transparent plastic film substrate and the hard coating layer during annealing treatment can be relaxed. disappear.

In addition, from a viewpoint of improving the adhesiveness with the laminated transparent conductive film or the optical adjustment layer mentioned later, and the adhesiveness with an adhesive agent, the ethylene oxide unit contained in one molecule of the polymerizable compound (B) The content of all alkylene oxide units is preferably 60 to 100 mole%, more preferably 75 to 100 mole%, still more preferably 85 to 100 mole%, and most preferably substantially 100 mole%.

n represents the number of alkylene oxide units, and each is independently an integer of 1 or more.

In addition, the above general formula (2) in one molecule of the polymerizable compound (B) The total value of n (the total number of alkylene oxide units in one molecule of the polymerizable compound (B)) is 3 or more, preferably 4 to 20, more preferably 6 to 16, and even more preferably 8 to 14. .

If the total value is 4 or more, it can be expected that softness is imparted to the obtained hard coat layer, and the deformation at the time of annealing treatment can be relaxed. Disappearing effect.

On the other hand, when the total value is more than 20, the rigidity of the hard coat layer may be insufficient, and the effect of suppressing thermal shrinkage of the transparent plastic film substrate may be insufficient.

The number of the groups represented by the general formula (2) contained in one molecule of the polymerizable compound (B) is 3 or more, preferably 3 to 16, more preferably 3 to 12, and even more preferably 3 to 10, more preferably 5-8.

If the number of the groups is less than 3, the crosslinking density of the obtained hard coat layer is lowered, and the surface hardness is lowered, which is not preferable.

On the other hand, when the number is 16 or less, it is possible to suppress a decrease in flexibility due to an excessively high crosslinking density, which is preferable.

Examples of such a polymerizable compound (B) include alkylene oxide-modified glycerol tri (meth) acrylate, alkylene oxide-modified dipentaerythritol tetra (meth) acrylate, and alkylene oxide-modified dipentaerythritol. Hexa (meth) acrylate and the like.

In addition, these (B) components can be used individually or in combination of 2 or more types.

In the curable resin, the weight ratio ((A) / (B)) of the component (A) to the component (B) is 15/85 to 85/15, preferably 20/80 to 80/20, and more preferably 28/72 ~ 72/28, more preferably 35/65 ~ 65/35, still more preferably 41/59 ~ 59/41, and still more preferably 46/54 ~ 54/46.

If the weight ratio is less than 15/85, since the amount of the (B) component is excessive, the surface hardness of the obtained hard coat layer is lowered, which is not preferable.

On the other hand, if the weight ratio is more than 85/15, it is considered that since the amount of the (A) component is excessive, the ability of the obtained hard coat layer to eliminate deformation due to heat is reduced.

(iii) Photopolymerization initiator (C) (hereinafter, sometimes referred to as (C) component)

In addition, from the viewpoint of efficiently curing the active energy ray-curable resin, a photopolymerization initiator (C) is preferably contained as necessary.

Examples of the photopolymerization initiator (C) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, Acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy- 2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) one, benzophenone, p-phenylbenzophenone, 4,4'-diethyl Aminobenzophenone, Dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2 -Ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzophenone dimethyl ketal, acetophenone dimethyl Methyl ketal, p-dimethylamine benzoate and the like.

In addition, these can be used individually by 1 type or in combination of 2 or more types.

The blending amount of the photopolymerization initiator (C) is preferably a value in the range of 0.2 to 10 parts by weight, and more preferably 1 to 100 parts by weight based on 100 parts by weight of the total of the components (A) and (B). A value within a range of 5 parts by weight.

(2) Composition for forming a hard coat layer

In addition, the hard coat layer is preferably prepared by preparing a composition for forming a hard coat layer in advance, and applying it as described later. Formed after drying.

This composition can be prepared by dissolving or dispersing an active energy ray-curable resin and various additive components as desired in an appropriate solvent at a predetermined ratio, as needed.

In addition, as various addition components, a silica particle, an antioxidant, an ultraviolet absorber, a (near) infrared absorber, a silane coupling agent, a light stabilizer, a leveling agent, a refractive index adjuster, etc. are mentioned, for example. Antistatic agents, defoamers, etc.

Examples of the solvent to be used include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and dichloroethane, methanol, ethanol, propanol, Alcohols such as butanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; and cellosolve solvents such as ethyl cellosolve Wait.

The concentration and viscosity of the composition for forming a hard coat layer prepared in this manner can be appropriately selected as long as it is within a range that can be applied.

Therefore, in general, from the viewpoint of easily adjusting the thickness of the obtained hard coat layer to a desired range, it is preferable to dilute it so that the solid content concentration becomes a value in the range of 0.05 to 10% by weight, and more preferably 0.1. Dilution is carried out in a manner ranging from a value of ~ 8% by weight.

(3) Thickness

The thickness of the hard coat layer is preferably a value in the range of 1 to 15 μm.

The reason is that if the thickness of the hard coat layer is less than 1 μm, the thermal shrinkage retention function of the transparent plastic film substrate by the annealing treatment is insufficient, and the occurrence of curl cannot be suppressed.

On the other hand, if the thickness of the hard coat layer is a value greater than 15 μm, exhaust gas may be generated from the hard coat layer due to the annealing treatment.

Therefore, the thickness of the hard coat layer is more preferably a value in the range of 1.5 to 10 μm, and more preferably a value in the range of 2 to 5 μm.

(4) Hardness

In addition, the pencil hardness of the hard coat layer measured based on JIS K 5600-5-4 is preferably in the range of 2B to 6H, more preferably in the range of HB to 5H, and even more preferably in the range of H to 4H.

3. Transparent conductive film

(1) Material substance

The material of the transparent conductive film is not particularly limited as long as it has both transparency and conductivity. Examples include indium oxide, zinc oxide, tin oxide, indium tin oxide (ITO), tin antimony oxide, and zinc aluminum. Oxide, indium zinc oxide, etc.

In addition, ITO is preferably used as a material substance.

The reason is that if it is ITO, a transparent conductive film having excellent transparency and conductivity can be formed by using appropriate film formation conditions.

(2) Thickness

The thickness of the transparent conductive film is preferably a value in a range of 5 to 500 nm.

The reason is that if the thickness of the transparent conductive film is less than 5 nm, not only the transparent conductive film becomes brittle, but sufficient conductivity may not be obtained. On the other hand, if the thickness of the transparent conductive film is more than 500 nm, the color due to the transparent conductive film may become dark, and the pattern shape of the transparent conductive film may be easily seen.

Therefore, a more preferable thickness of the transparent conductive film is a value in a range of 15 to 250 nm, and a value in a range of 20 to 100 nm is more preferable.

(3) Electrical conductivity

In addition, the surface resistance of the transparent conductive film after the annealing treatment is preferably a value in a range of 10 to 1000 Ω / □, more preferably a value in a range of 50 to 500 Ω / □, and still more preferably 100 to 300 Ω / □. Value in the range.

4.Optical adjustment layer

As a second embodiment, as shown in FIG. 1b, the transparent conductive film 1 and the first hard coat layer 2a in the transparent conductive film 10 with a protective film according to the first embodiment may be preferably mentioned. A configuration in which an optical adjustment layer 8 is provided at intervals. This is because the pattern shape of the transparent conductive film 1 caused by the difference between the refractive index of the transparent conductive film 1 and the refractive index of the first hard coat layer 2 a can be made difficult to be seen by providing the optical adjustment layer 8.

Here, as shown in FIG. 1b, the optical adjustment layer 8 is preferably laminated on the first hard coat layer 2a with a high-refractive index layer 8a having a relatively high refractive index and a folding layer in this order. The low refractive index layer 8b having a relatively low emissivity is formed.

Hereinafter, the high refractive index layer 8 a and the low refractive index layer 8 b constituting the optical adjustment layer 8 will be described.

(1) High refractive index layer

(1) -1 refractive index

The refractive index of the high refractive index layer is preferably 1.6 or more and less than 2.

The reason is that if the refractive index of the high refractive index layer is less than 1.6, a meaningful refractive index difference from the low refractive index layer may not be obtained, and the pattern shape of the transparent conductive film may be easily seen. On the other hand, if the refractive index of the high refractive index layer is a value of 2 or more, the film of the high refractive index layer may become brittle.

Therefore, the refractive index of the high refractive index layer is more preferably 1.6 or more and less than 1.9, and still more preferably 1.6 or more and less than 1.8.

(1) -2 thickness

The thickness of the high refractive index layer is preferably 20 to 130 nm.

The reason is that if the thickness of the high refractive index layer is less than 20 nm, the film of the high refractive index layer may become brittle and the shape of the layer may not be maintained. On the other hand, if the thickness of the high refractive index layer is a value larger than 130 nm, the pattern shape of the transparent conductive film may be easily seen in some cases.

Therefore, the thickness of the high refractive index layer is more preferably 23 to 120 nm, and still more preferably 30 to 110 nm.

(1) -3 material substance

In addition, the high refractive index layer is preferably made of metal oxide fine particles. It is composed of a cured product of a composition of an active energy ray-curable compound.

The reason is that by including metal oxide fine particles, it is easy to adjust the refractive index of the high refractive index layer.

(i) Metal oxide particles

Examples of the type of metal oxide include tantalum oxide, zinc oxide, indium oxide, hafnium oxide, cerium oxide, tin oxide, niobium oxide, indium tin oxide (ITO), and antimony tin oxide (ATO).

In addition, from the viewpoint of achieving high refractive index without lowering the transparency, it is particularly preferably at least one selected from the group consisting of titanium oxide and zirconia.

In addition, these metal oxides may be used individually by 1 type, and may use 2 or more types together.

The average particle diameter of the metal oxide fine particles is preferably a value in the range of 0.005 μm to 1 μm. The average particle diameter of the metal oxide fine particles can be obtained by, for example, a measurement method using a Zeta potential measurement method.

The compounding amount of the metal oxide fine particles is preferably 20 to 2000 parts by weight, more preferably 80 to 1,000 parts by weight, and still more preferably 150 to 400 parts by weight based on 100 parts by weight of the active energy ray-curable compound described later. .

(ii) Active energy ray-curable compounds

The active energy ray-curable compound used for the formation of the high-refractive index layer refers to a polymerizable compound that is cross-linked and cured by irradiating a substance having an energy quantum in an electromagnetic wave or a charged particle beam, that is, ultraviolet rays or electron beams, for example Examples include photopolymerizable prepolymers and photopolymerizable monomers.

The photopolymerizable prepolymer includes a radical polymerization type and a cation polymerization type. Examples of the radical polymerization type photopolymerizable prepolymer include polyester acrylates, epoxy acrylates, and urethanes. Ester acrylate, polyol acrylate and the like.

Examples of the polyester acrylate prepolymer include esterification of hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polycarboxylic acid and a polyhydric alcohol with (meth) acrylic acid. Or a compound obtained by esterifying a terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid with (meth) acrylic acid.

Examples of the epoxy acrylate-based prepolymer include esterification of a lower molecular weight bisphenol-type epoxy resin and a novolak-type epoxy resin with an ethylene oxide ring of (meth) acrylic acid. And the resulting compound.

Examples of the urethane acrylate-based prepolymer include, for example, a polyurethane obtained by reacting a polyether polyol, a polyester polyol, and a polyisocyanate with (meth) acrylic acid. A compound obtained by esterifying an ester oligomer.

Examples of the polyol acrylate-based prepolymer include compounds obtained by esterifying a hydroxyl group of a polyether polyol with (meth) acrylic acid.

In addition, these polymerizable prepolymers may be used individually by 1 type, and may be used in combination of 2 or more type.

On the other hand, as a cationically polymerizable photopolymerizable prepolymer, an epoxy resin is generally used.

Examples of the epoxy resin include compounds obtained by epoxidizing polyphenols such as bisphenol resins and novolac resins with epichlorohydrin, and linear olefin compounds and cyclic compounds with peroxides. A compound obtained by oxidizing an olefin compound.

Examples of the photopolymerizable monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol di (methyl) Base) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, di Cyclopentyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphate di (meth) acrylate, allyl cyclohexyl Di (meth) acrylate, isocyanurate di (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified three Methylolpropane tri (meth) acrylate, tris (propenyloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate And polyfunctional acrylates such as caprolactone-modified dipentaerythritol hexa (meth) acrylate.

In addition, these photopolymerizable monomers may be used individually by 1 type, and may use 2 or more types together.

(iii) Photopolymerization initiator

From the viewpoint of efficiently curing the active energy ray-curable compound, it is preferable to use a photopolymerization initiator in combination as necessary.

Examples of the photopolymerization initiator include radical polymerization type photopolymerizable prepolymers and photopolymerizable monomers, such as benzoin and benzene. Parylene methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxy ring Hexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one, 4- (2-hydroxyethoxy) phenyl-2 (Hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone , 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-bis Methylthioxanthone, 2,4-diethylthioxanthone, benzophenone dimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate, and the like.

Examples of the photopolymerization initiator for the cationic polymerizable photopolymerizable prepolymer include oniums such as aromatic sulfonium ions, aromatic oxonium ions, and aromatic iodonium ions, and tetrafluoroborate salts. Compounds composed of anions such as hexafluorophosphate, hexafluoroantimonate, and hexafluoroarsenate.

In addition, these can be used individually by 1 type or in combination of 2 or more types.

The blending amount of the photopolymerization initiator is preferably a value in the range of 0.2 to 10 parts by weight, and more preferably in the range of 1 to 5 parts by weight, relative to 100 parts by weight of the active energy ray-curable compound. Value.

(1) -4 Composition for forming high refractive index layer

The high-refractive index layer is preferably prepared by preparing a composition for forming a high-refractive index layer in advance, and coating it as described later. Formed after drying.

The composition can be prepared by: In an appropriate solvent, an active energy ray-curable compound, a photopolymerization initiator, and various additive components used as necessary are added and dissolved or dispersed.

In addition, examples of the various additive components include antioxidants, ultraviolet absorbers, (near) infrared absorbers, silane-based coupling agents, light stabilizers, leveling agents, antistatic agents, and antifoaming agents.

Examples of the solvent to be used include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and dichloroethane, methanol, ethanol, propanol, Alcohols such as butanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; and cellosolve solvents such as ethyl cellosolve Wait.

The concentration and viscosity of the composition for forming a high-refractive-index layer thus prepared are not particularly limited as long as they can be applied, and they can be appropriately selected according to circumstances.

Therefore, from the viewpoint of easily adjusting the film thickness of the obtained high-refractive index layer to a predetermined range, it is preferred to dilute it at a solid content concentration of 0.05 to 10% by weight, and more preferably to dilute it at 0.1 to 8% by weight. .

(2) Low refractive index layer

(2) -1 refractive index

The refractive index of the low refractive index layer is preferably 1.3 or more and less than 1.6.

The reason is that if the refractive index of the low refractive index layer is less than 1.3, the film of the low refractive index layer may become brittle. On the other hand, if the discount When the refractive index of the emissivity layer is a value of 1.6 or more, a meaningful refractive index difference from the high refractive index layer may not be obtained, and the pattern shape of the transparent conductive film may be easily seen.

Therefore, the refractive index of the low refractive index layer is more preferably 1.3 or more and less than 1.5, and even more preferably 1.3 or more and less than 1.45.

(2) -2 thickness

The thickness of the low refractive index layer is preferably 10 to 150 nm.

The reason is that if the thickness of the low refractive index layer is less than 10 nm, the film of the low refractive index layer may become brittle and the shape of the layer may not be maintained. On the other hand, if the thickness of the low-refractive index layer is a value larger than 150 nm, the pattern shape of the transparent conductive film may be easily seen in some cases.

Therefore, the thickness of the low refractive index layer is more preferably 15 to 135 nm, and still more preferably 20 to 120 nm.

(2) -3 material substance

The low refractive index layer is preferably composed of a cured product of a composition containing silicon dioxide particles and an active energy ray-curable compound.

The reason is that the inclusion of silicon dioxide particles makes it easy to adjust the refractive index of the low refractive index layer.

As the silica particles, hollow silica particles or porous silica particles are preferred.

The reason is that if the hollow silica particles or porous silica particles are used, the refractive index of the low refractive index layer can be more effectively reduced to a predetermined range.

In addition, in order to exert the effect as a low refractive index layer, The average particle diameter of the silicon dioxide fine particles is preferably 1 μm or less, and more preferably a value in the range of 10 to 100 nm. In addition, the average particle diameter of a silicon dioxide microparticles | fine-particles can be calculated | required by a Zeta potential measurement method, for example.

In addition, the blending amount of the silica particles is preferably 50 to 500 parts by weight, more preferably 80 to 300 parts by weight, and still more preferably 100 to 250 parts by weight relative to 100 parts by weight of the active energy ray-curable compound. Serving.

(2) -4 Composition for forming a low refractive index layer

The low-refractive-index layer is preferably prepared by preparing a composition for forming a low-refractive-index layer in advance, and coating it as described later. Formed after drying.

The composition can be prepared by adding, as necessary, the above-mentioned silica particles, an active energy ray-curable compound, a photopolymerization initiator, and various additives used as necessary in an appropriate solvent at a predetermined ratio. Ingredients to make it dissolve or disperse.

In addition, the concentration, viscosity, etc. of various additive components, solvents, and a composition for forming a low-refractive-index layer are the same as those described in the description of the high-refractive-index layer.

(3) Characteristics of the optical adjustment layer

As described above, the second embodiment in which the optical adjustment layer is provided between the transparent conductive film and the first hard coat layer has the effect of making the pattern-shaped transparent conductive film difficult to see. In addition, the transparent conductive film with a protective film of this embodiment can maintain the effect that the pattern shape of the transparent conductive film is not easily seen even after the annealing treatment.

Specifically, a general transparent conductive film has When the optical adjustment layer is provided, the pattern shape of the transparent conductive film after annealing treatment is also a significant problem. It is considered that this is because the thermal contraction rate of the transparent conductive film portion made of an inorganic material is small and the thermal shrinkage rate of the optical adjustment layer portion made of an organic material is large. The boundary of the existing part is deformed.

In contrast, the transparent conductive film with a protective film of the present invention suppresses the occurrence of curl by suppressing thermal contraction of the transparent plastic film substrate. Therefore, in the second embodiment, the thermal shrinkage of the transparent plastic film substrate is suppressed. Therefore, in the second embodiment, the pattern shape of the transparent conductive film can be made difficult to be seen even after the annealing treatment.

From the viewpoint of further exerting such an effect, it is preferable that the thermal shrinkage ratios in the MD direction and the TD direction of the transparent plastic film substrate are both 0.5% or less, and particularly preferably 0.3% or less.

From the same viewpoint, the absolute value of the curl value is preferably 30 mm or less, and particularly preferably 15 mm or less.

5. Protective film

(1) Protective film substrate

(1) -1 type

The resin used in the protective film substrate is not particularly limited as long as it can improve the workability by being laminated on a transparent conductive film, and examples thereof include polyethylene terephthalate (PET) and polyethylene naphthalate. Polyester resins such as glycol esters, polyolefin resins such as polypropylene, and paper.

Among them, polyester-based resins and polyolefin-based resins are more preferred.

(1) -2 Thermal shrinkage

In the present invention, the protective film substrate is characterized in that the heat shrinkage rate in the MD direction when heated at 150 ° C. for 60 minutes is a value of 0.6% or less.

The reason is that in combination with the predetermined heat shrinkage characteristics of the transparent plastic film base material described above, the occurrence of curl can be effectively suppressed even when the annealing treatment is performed in the state of the transparent conductive film with a protective film.

That is, if the thermal shrinkage ratio of the protective film substrate in the MD direction is greater than 0.6%, it may be difficult to effectively suppress the occurrence of curl regardless of the difference from the thermal shrinkage ratio of the transparent plastic film substrate in the MD direction. . On the other hand, in order to make the thermal shrinkage ratio of the protective film base material in the MD direction too small, it may be necessary to add particles or the like or to mix a material having excellent heat resistance, and thus the generation of exhaust gas during annealing treatment becomes a problem.

Therefore, it is more preferable that the thermal shrinkage of the protective film substrate in the MD direction when heated at 150 ° C. for 60 minutes is a value in the range of 0.01 to 0.6%, and more preferably a value in the range of 0.1 to 0.5%.

Here, the relationship between the thermal shrinkage of the protective film substrate in the MD direction and the curl value of the transparent conductive film with the protective film will be described using FIG. 3.

That is, FIG. 3 shows the thermal shrinkage (%) in the MD direction of the protective film substrate when heated at 150 ° C. for 60 minutes as the horizontal axis, and the curl value (mm) of the transparent conductive film with the protective film. ) Is a scatter plot for the vertical axis.

In addition, the transparent conductive film with a protective film as a measurement target was manufactured using Examples 1-5 and Comparative Example 3 mentioned later. Into a transparent conductive film.

That is, a transparent conductive film with a protective film such as a transparent plastic film base material having a thermal shrinkage ratio in the MD direction of 0.6% or less is used as a measurement target.

From the scatter diagram, it can be seen that under the condition that the thermal shrinkage rate of the transparent plastic film substrate in the MD direction is 0.6% or less, if the thermal shrinkage rate of the protective film substrate in the MD direction is 0.6% or less, then The curl value can be controlled within a substantially allowable range of about -20 to 20 mm.

On the other hand, even if the thermal shrinkage ratio of the transparent plastic film substrate in the MD direction is 0.6% or less, it can be seen that if the thermal shrinkage ratio of the protective film substrate in the MD direction is more than 0.6%, curling occurs. When the value becomes a value smaller than -40 mm or larger than 40 mm, it cannot be controlled within a substantially allowable range, which causes a problem.

Therefore, it can be understood from the scatter diagram shown in FIG. 3 that from the viewpoint of effectively suppressing the occurrence of curling of the transparent conductive film with a protective film, the thermal shrinkage rate in the MD direction of the transparent plastic film substrate needs to be 0.6%. Under the conditions of the following values, the thermal shrinkage of the protective film substrate in the MD direction is a value of 0.6% or less.

In addition, considering both the scattergrams of FIGS. 2 and 3, it can be understood that in order to effectively suppress the occurrence of curling of the transparent conductive film with a protective film, it is necessary to make the transparent plastic film substrate heat in the MD direction. The shrinkage ratio is a value of 0.6% or less, and the thermal shrinkage ratio of the protective film substrate in the MD direction is a value of 0.6% or less.

Next, the relationship between the difference in thermal shrinkage of the transparent plastic film substrate and the protective film substrate in the MD direction and the curl value will be described using FIG. 4.

That is, FIG. 4 shows that the difference (%) obtained by subtracting the thermal shrinkage ratio (%) of the protective film substrate in the MD direction from the thermal shrinkage ratio (%) of the transparent plastic film substrate in the MD direction is horizontal. The axis is a scattergram formed by taking the curl value (mm) of a transparent conductive film with a protective film as the vertical axis.

In addition, as a transparent conductive film with a protective film as a measurement target, the transparent conductive films prepared as Examples 1-5 and Comparative Examples 1-3 mentioned later were used.

It can be understood from the scatter diagram described above that there is a clear correlation between the difference in thermal shrinkage in the MD direction of the transparent plastic film substrate and the protective film substrate and the curl value.

More specifically, it can be seen that even when the absolute value of the difference between the thermal shrinkage ratios in the MD direction of the transparent plastic film substrate and the protective film substrate is small, the curl value may be large. On the contrary, even if the When the absolute value of the difference between the heat shrinkage ratios is large, the curl value may be small.

The reason is considered that when the difference in the heat shrinkage rate in the MD direction is small and the difference is the same, the difference in the heat shrinkage rate in the TD direction also affects.

However, when the thermal shrinkage of the transparent plastic film base material in the MD direction is 0.6% or less and the protective film base material has a heat shrinkage ratio of 0.6% or less in the MD direction, the difference is set to a predetermined range. This value can suppress the occurrence of curl more effectively.

Therefore, it is preferable to heat the transparent plastic film substrate at 150 ° C. The difference between the heat shrinkage rate in the MD direction at 60 minutes and the heat shrinkage rate in the MD direction of the protective film substrate when heated at 150 ° C for 60 minutes is a value in the range of -0.5 to 0.5%, more preferably -0.4 to A value in the range of 0.4% is more preferably a value in the range of -0.3 to 0.3%.

In addition, the thermal shrinkage ratio of the protective film substrate when heated at 150 ° C. for 60 minutes is preferably a value of 0.6% or less.

The reason is that the thermal shrinkage of the protective film substrate in the TD direction is a value within the above range, so that the occurrence of curl can be further effectively suppressed even when the annealing treatment is performed.

That is, if the thermal shrinkage rate in the TD direction is greater than 0.6%, it may be difficult to effectively suppress the occurrence of curl regardless of the difference from the thermal shrinkage rate in the TD direction of the transparent plastic film substrate. On the other hand, in order to make the thermal shrinkage ratio of the protective film base material in the TD direction too small, it may be necessary to add particles or the like or to mix materials with excellent heat resistance, and thus the generation of exhaust gas during annealing treatment becomes a problem.

Therefore, it is more preferable that the thermal shrinkage ratio of the protective film substrate in the TD direction when heated at 150 ° C. for 60 minutes is in a range of 0.01 to 0.5%, and more preferably a value in a range of 0.02 to 0.3%.

(1) -3 thickness

The thickness of the protective film substrate is preferably a value in a range of 10 to 300 μm.

The reason is that if the thickness of the protective film substrate is less than 10 μm, the effect of suppressing curling of the transparent conductive film during annealing may be insufficient. On the other hand, if the thickness of the protective film substrate is If the value is larger than 300 μm, the protective film substrate itself may have a heat distribution in the thickness direction after the annealing treatment, and thus the protective film substrate may curl.

Therefore, the thickness of the protective film substrate is more preferably a value in a range of 30 to 200 μm, and more preferably a value in a range of 50 to 150 μm.

(2) Adhesive layer

(2) -1 material substance

The adhesive used in the adhesive layer is not particularly limited, and a conventionally known adhesive can be used.

For example, a binder that uses the following polymers as the base polymer may be appropriately selected and used, that is, acrylic polymer, silicone polymer, polyester, polyurethane, polyamide, polyvinyl ether, vinyl acetate / vinyl chloride copolymer , Modified polyolefin, epoxy-based, fluorine-based, natural rubber, synthetic rubber and other rubber-based polymers.

(2) -2 thickness

The thickness of the adhesive layer is preferably a value in a range of 2 to 50 μm.

The reason is that if the thickness of the adhesive layer is less than 2 μm, the adhesive force may be insufficient. On the other hand, if the thickness of the adhesive layer is more than 100 μm, the exhaust of the adhesive layer may be a problem.

Therefore, the thickness of the adhesive layer is more preferably a value in a range of 5 to 50 μm, and more preferably a value in a range of 10 to 30 μm.

6.Curl value

In addition, the transparent conductive film with a protective film of the present invention is cut out into a square of 100 mm in the MD direction and 100 mm in the TD direction, and is heated at 150 ° C. for 60 minutes with the protective film side as the lower side. The value is 25 mm or less.

The reason is that the absolute value of the curl value measured by a predetermined method is a value within the above range, so that the occurrence of curl can be more effectively suppressed even when the annealing process is performed.

That is, if the absolute value of the said curl value is a value larger than 25 mm, it may become a problem in actual use.

The lower limit of the absolute value of the curl value is 0 mm.

Therefore, a square of 100 mm in the MD direction and 100 mm in the TD direction is cut out, and the protective film side is lowered and heated at 150 ° C. for 60 minutes. The absolute value of the curl value at this time is preferably 22 mm or less, and more preferably 15 mm. The following values.

In addition, when the optical adjustment layer is provided as described above, if the absolute value of the curl value is in the above range, it is possible to effectively prevent a change in the visibility of the pattern of the transparent conductive film after the annealing treatment.

7. Manufacturing method of transparent conductive film

The transparent conductive film of the present invention can be obtained by a production method including the following steps (a) to (g).

(a) A step of preparing a transparent plastic film substrate having a heat shrinkage ratio in the MD direction of 0.6% or less when heated at 150 ° C for 60 minutes

(b) Forming a first hard coat on one side of a transparent plastic film substrate Layer steps

(c) a step of forming a second hard coat layer on the other side of the transparent plastic film substrate

(d) a step of forming a transparent conductive film on the first hard coat layer to obtain a transparent conductive film

(e) A step of preparing a protective film substrate having a heat shrinkage ratio in the MD direction of 0.6% or less when heated at 150 ° C for 60 minutes.

(f) a step of forming an adhesive layer on one side of the protective film substrate to obtain a protective film

(g) A step of bonding the adhesive layer in the protective film to the second hard coat layer in the transparent conductive film to obtain a transparent conductive film with a protective film

In the following, the same portions as those described above are omitted, and only the different portions will be described in detail.

(1) Step (a): Step of preparing a transparent plastic film substrate

A transparent plastic film substrate having a heat shrinkage ratio in the MD direction when heated at 150 ° C for 60 minutes was prepared to a value of 0.6% or less.

It should be noted that the details of the transparent plastic film substrate have already been described, and are therefore omitted.

(2) Step (b): a step of forming a first hard coat layer

In one side of the transparent plastic film substrate prepared in step (a), the above-mentioned composition for forming a hard coat layer is applied by a conventionally known method to form a coating film, followed by drying, and irradiating it with active energy rays to apply the coating. The film was cured, thereby forming a first hard coat layer.

Examples of the method for applying the composition for forming a hard coat layer include a bar coating method, a blade coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method.

The drying conditions of the coating film are preferably performed at 60 to 150 ° C. for about 10 seconds to 10 minutes.

Examples of the active energy rays include ultraviolet rays and electron beams.

In addition, examples of the ultraviolet light source include a high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, and a xenon lamp. The irradiation amount thereof is usually preferably 100 to 500 mJ / cm ² .

On the other hand, as a light source of the electron beam, an electron beam accelerator or the like is mentioned, and the irradiation amount thereof is generally preferably 150 to 350 kV.

(3) Step (c): Step of forming a second hard coat layer

On the other side of the transparent plastic film substrate prepared in step (a), a composition for forming a hard coat layer is applied to form a coating film in the same manner as the formation of the first hard coat layer, and then dried to irradiate the active layer. The energy ray hardens the coating film, thereby forming a second hard coat layer.

(4) Step (c ′): a step of forming an optical adjustment layer

If necessary, a step of forming an optical adjustment layer may be provided after step (c) as step (c ′). The effect produced by providing the optical adjustment layer is as described above.

That is, on the surface of the first hard coat layer formed in the above step, the composition for forming the high-refractive index layer is applied by a conventionally known method to form a coating film, followed by drying, and irradiating the coating with an active energy ray. solid To form a high refractive index layer.

Examples of the coating method of the composition for forming a high refractive index layer include a bar coating method, a blade coating method, a roll coating method, a doctor blade coating method, a die coating method, and a gravure coating method.

The drying conditions are preferably performed at 60 to 150 ° C. for about 10 seconds to 10 minutes.

Examples of the active energy rays include ultraviolet rays and electron beams.

In addition, examples of the ultraviolet light source include a high-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, and a xenon lamp. The irradiation amount thereof is usually preferably 100 to 500 mJ / cm ² .

On the other hand, as a light source of the electron beam, an electron beam accelerator or the like is mentioned, and the irradiation amount thereof is generally preferably 150 to 350 kV.

Next, a low refractive index layer is formed on the formed high refractive index layer.

That is, the low-refractive-index layer is the same as the case of forming the high-refractive-index layer on the hard coat layer 1, and can be applied. The composition for forming the low-refractive index layer is dried, and is irradiated with active energy rays to be cured.

(5) Step (d): Step of forming a transparent conductive film

For the first hard coat layer (or the optical adjustment layer formed in step (c ′)) formed in step (b), a vacuum evaporation method, a sputtering method, a CVD method, an ion plating method, a spray method, and a sol- A known method such as a gel method is used to form a transparent conductive film to obtain a transparent conductive film.

In addition, as a sputtering method, a general method using a compound is mentioned. A common sputtering method, or a reactive sputtering method using a metal target.

In this case, as the reactive gas, oxygen, nitrogen, water vapor, or the like is preferably introduced, or ozone addition, ion assist, or the like is used in combination.

In addition, the transparent conductive film can be formed into a linear pattern or the like by forming a resist mask in a predetermined pattern by a photolithography method after forming the film as described above, and then performing an etching process by a known method.

In addition, as an etching liquid, the aqueous solution of acids, such as hydrochloric acid, a sulfuric acid, nitric acid, and phosphoric acid, etc. are mentioned preferably.

(6) Step (e): Step for preparing a protective film substrate

When heated at 150 ° C. for 60 minutes, a protective film substrate having a heat shrinkage ratio in the MD direction of 0.6% or less was prepared.

In addition, since the details of the protective film substrate have already been described, they are omitted.

(7) Step (f): a step of forming an adhesive layer

One side of the protective film substrate prepared in step (e) is coated with an adhesive composition by a conventionally known method to form a coating film, and then dried or irradiated with an active energy ray to form an adhesive layer to be protected. film.

Examples of the method for applying the adhesive composition include a bar coating method, a blade coating method, a roll coating method, a doctor blade coating method, a die coating method, and a gravure coating method.

(8) Step (g): bonding step

The adhesive layer in the protective film obtained in step (f) and the second hard coat layer in the transparent conductive film obtained in step (d) were laminated to obtain To a transparent conductive film with a protective film.

At this time, bonding is performed so that the MD direction of the transparent conductive film and the MD direction of the protective film base material match.

In addition, as a bonding method, bonding can be performed using a laminator, for example.

Examples

Hereinafter, the transparent conductive film of this invention is demonstrated in detail with reference to an Example.

[Example 1]

1. Manufacturing of transparent conductive film with protective film

(1) Preparation of transparent plastic film substrate

As a transparent plastic film substrate, a PET film having a thickness of 60 μm, a thermal shrinkage of 0.26% in the MD direction, and a thermal shrinkage of 0% in the TD direction was prepared.

Here, the thermal shrinkage of a transparent plastic film substrate is measured as follows.

That is, a square of 110 mm in the MD direction and 110 mm in the TD direction was cut out from a transparent plastic film substrate as a test piece.

Next, on the obtained test piece, a square of 100 mm in the MD direction and 100 mm in the TD direction was marked with a ballpoint pen.

Next, using a digital micrometer (MODEL AT112, manufactured by Mitutoyo Corporation), the length X (μm) of one side in the MD direction among the four sides of the square marked with a ballpoint pen was measured.

Next, the test piece was placed in a hot air loop oven at 150 ° C. Let stand for 60 minutes.

Then, the test piece was taken out from the hot-air loop oven, and the length Y (μm) of one side in the MD direction was measured with a digital micrometer on the side of the square marked with a ball-point pen and the side whose length was previously measured.

Then, the heat shrinkage rate in the MD direction was calculated using the following calculation formula (1).

In addition, similarly to the heat shrinkage rate in the MD direction, the heat shrinkage rate in the TD direction was also calculated.

(X-Y) / X × 100 = Thermal shrinkage (%) (1)

(2) Preparation of composition for forming hard coat layer

70 parts by weight of pentaerythritol triacrylate (trade name "A-TMM-3L" manufactured by Shin Nakamura Chemical Industry Co., Ltd.) as a polymerizable compound (A) (representing a solid content conversion value, the same below), and as a polymerizable compound (B) 30 parts by weight of ethylene oxide-modified dipentaerythritol hexaacrylate (produced by Shin Nakamura Chemical Co., Ltd., trade name "A-DPH-12E") as a photopolymerization initiator, 1-hydroxycyclohexylphenyl 5 parts by weight of ketone (manufactured by BASF, trade name "IRGACURE 184") and 0.2 weight by weight of a silicone-modified acrylic polymer-based leveling agent (manufactured by BYK-Chemie Japan, trade name "BYK-3550") Parts were mixed to prepare an active energy ray-curable resin, and then diluted with propylene glycol monomethyl ether to obtain a composition for forming a hard coat layer having a solid content concentration of 30% by weight.

(3) Formation of hard coating

Next, the surface of the prepared transparent plastic film substrate was coated with a composition for forming a hard coat layer with a wire rod # 4.

Next, after drying in an oven at 70 ° C. for 1 minute, a high-pressure mercury lamp was used to irradiate ultraviolet rays of 200 mJ / cm ² in a nitrogen atmosphere to form a first hard coat layer having a thickness of 3 μm and a pencil hardness H on the surface of a transparent plastic film substrate. .

Next, the surface of the transparent plastic film substrate on the side opposite to the side on which the first hard coating layer was formed was coated with a wire rod # 4 with a composition for forming the same hard coating layer as the first hard coating layer.

Next, after drying in an oven at 70 ° C for 1 minute, a high-pressure mercury lamp was used to irradiate ultraviolet rays of 200 mJ / cm ² in a nitrogen atmosphere to form a second hard coating layer having a thickness of 3 μm and a pencil hardness H on the surface of the transparent plastic film substrate .

(4) Formation of optical adjustment layer

(4) -1 Preparation of composition for forming high refractive index layer

30 parts by weight of a high refractive index coating agent (manufactured by Atomix Corporation, Atomcompobrid HUV SRZ100 containing nano-sized zirconia particles as a high refractive index agent) and 0.9 parts by weight of a photopolymerization initiator (IRGACURE907 manufactured by BASF Corporation) And 0.02 parts by weight of a leveling agent (by BYK Chemie, BYK-355), and diluted with 1493 parts by weight of methyl isobutyl ketone and 1493 parts by weight of cyclohexanone to prepare a solid content concentration of 1 weight % High refractive index layer forming composition.

(4) -2 Preparation of composition for forming low refractive index layer

100 parts by weight of a hard coating agent (manufactured by Arakawa Chemical Industry Co., Ltd., BEAMSET 575CB), 98 parts by weight of a hollow silica sol (manufactured by Nippon Kasei Kasei Co., Ltd., Sururia 4320, average particle diameter 50 nm), and a photopolymerization initiator (BASF Co., Ltd., IRGACURE907) 0.9 parts by weight, and a leveling agent (BYK Chemie Co., Ltd., BYK-355) 0.05 parts by weight The composition was diluted with 9700 parts by weight of methyl isobutyl ketone and 9700 parts by weight of cyclohexanone to prepare a composition for forming a low refractive index layer having a solid content concentration of 1% by weight.

In addition, the composition of a hard coating agent (made by Arakawa Chemical Industries, Ltd., BEAMSET 575CB) is as follows.

(4) -3 Formation of high refractive index layer

A composition for forming a high refractive index layer was coated on the first hard coat layer with a bar # 4.

Then, after drying in an oven at 70 ° C. for 1 minute, a high-pressure mercury lamp was used to irradiate ultraviolet rays of 200 mJ / cm ² in a nitrogen atmosphere to form a high refractive index layer having a thickness of 23 nm and a refractive index of 1.87 on the hard coat layer.

(4) -4 Formation of low refractive index layer

Next, on the formed high refractive index layer, a composition for forming a low refractive index layer was coated with a wire rod # 4.

Next, after drying in an oven at 70 ° C. for 1 minute, a high-pressure mercury lamp was used to irradiate ultraviolet rays of 200 mJ / cm ² in a nitrogen atmosphere to form a low refractive index layer having a thickness of 74 nm and a refractive index of 1.39 on the high refractive index layer. An optical adjustment layer having a two-layer structure was formed on the coating.

(5) Formation of transparent conductive film

Next, the PET film on which the first and second hard coat layers and the optical adjustment layer were formed was cut into a length of 100 mm × width of 100 mm, and then an ITO target (oxygen) was used. 10% by weight of tin and 90% by weight of indium oxide) were sputtered on the optical adjustment layer to form a transparent conductive material having a square of 60 mm × 60 mm in the center of the optical adjustment layer, a thickness of 30 nm, and a surface resistance of 250 Ω / □. membrane.

Next, a photoresist film patterned in a grid pattern is formed on the surface of the obtained transparent conductive film.

Next, the photoresist film was removed by immersing in 10% by weight of hydrochloric acid for 1 minute at room temperature to perform an etching treatment, thereby obtaining a transparent conductive film having a patterned transparent conductive film.

The transparent conductive film has a transparent conductive film on the front surface of the optical adjustment layer. The transparent conductive film has a square gap of 2 mm on one side and is divided into a grid-like pattern shape by a transparent conductive line portion having a line width of 2 mm. The thickness is 30 nm.

(6) Preparation of protective film substrate

As a protective film substrate, a PET film having a thickness of 135 μm, a thermal shrinkage in the MD direction of 0.55%, and a thermal shrinkage in the TD direction of 0.04% was prepared.

In addition, the thermal shrinkage rate of a protective film base material was measured similarly to the thermal shrinkage rate of a transparent plastic film base material.

(7) Formation of adhesive layer

Next, 100 parts by weight of an acrylic polymer composed of butyl acrylate: acrylic acid = 100: 6 (weight ratio) having a weight average molecular weight of 600,000 and a monomer component ratio (weight ratio) contained an epoxy-based crosslinking agent (Mitsubishi "TETRAD C" manufactured by Gas Chemical Co., Ltd.) 6 parts by weight of the binder composition was diluted with ethyl acetate to a solid content concentration of 30% by weight, and applied to the prepared protective sheet. The surface of the film substrate. Then, it dried at 90 degreeC for 1 minute, and aged at 25 degreeC for 7 days. Thus, a protective film having an adhesive layer with a gel fraction of 95% by weight and a thickness of 20 μm was obtained.

(8) Lamination of protective film

Next, the second hard-coat layer in the transparent conductive film and the adhesive layer in the protective film were bonded using a laminator to form a transparent conductive film with a protective film.

At this time, bonding is performed so that the MD direction of the transparent plastic film substrate and the MD direction of the protective film substrate coincide.

2. Evaluation of curl

The occurrence of curl in the obtained transparent conductive film with a protective film was evaluated.

That is, the obtained transparent conductive film with a protective film was placed in a furnace at a temperature of 150 ° C. for 60 minutes with the protective film side as the lower side.

Thereafter, the test piece was taken out of the furnace, and the protective film side was set to the lower side under a temperature of 23 ° C. and a humidity of 50% RH on a glass plate for 60 minutes.

Then, the floating amount of the four angular distance glass plate surfaces of the test piece in the vertical direction was measured with a vernier caliper, and the maximum value among the obtained floating amounts was taken as the curl value. The obtained results are shown in Table 1.

In addition, since the value marked with a negative sign is opposite to the direction of curl, the front and back are reversed, and the curl value is measured similarly.

3. Visibility Evaluation of Patterned Transparent Conductive Film (Pattern Shape visibility)

The protective film was peeled from the transparent conductive film with a protective film used for curl evaluation, and the visibility of the pattern shape of the transparent conductive film was evaluated.

Specifically, a transparent conductive film is placed at a distance of 1 m from the white fluorescent lamp, and in a state where the white fluorescent lamp is reflected on the transparent conductive film, the distance between the transparent conductive film and the white fluorescent lamp is on the same side as the white fluorescent lamp. The transparent conductive film was visually observed at a position of 30 cm for deformation.

Then, the observation results obtained were evaluated according to the following judgment criteria. The obtained results are shown in Table 1.

In addition, as a practical use method of the transparent conductive film, generally, two transparent conductive films having a transparent conductive film patterned in a linear pattern are rotated and arranged by 90 ° to form a grid-like pattern. In the evaluation, for the sake of simplicity, the transparent conductive film in one transparent conductive film was formed into a grid pattern and evaluated.

(Double-circle): It was evaluated that all three appraisers could not see a pattern under reflected light.

：: Two of the three evaluators did not see a pattern under reflected light.

×: It was evaluated that two or more of the three evaluators could see a pattern under reflected light.

[Example 2]

In Example 2, a PET film having a thickness of 60 μm, a thermal shrinkage of 0.14% in the MD direction, and a thermal shrinkage of 0.32% in the TD direction was used as a transparent plastic film substrate. A tape was produced in the same manner as in Example 1. Have The transparent conductive film of the protective film was evaluated. The obtained results are shown in Table 1.

[Example 3]

In Example 3, as the transparent plastic film substrate, a PET film having a thickness of 60 μm, a thermal shrinkage of 0.14% in the MD direction and a thermal shrinkage of 0.32% in the TD direction was used, and a protective film substrate was used with a thickness of 135 μm and MD Except for the PET film having a thermal shrinkage of 0.51% and a thermal shrinkage of 0.2% in the TD direction, a transparent conductive film with a protective film was produced in the same manner as in Example 1 and evaluated. The obtained results are shown in Table 1.

[Example 4]

In Example 4, as the transparent plastic film substrate, a PET film having a thickness of 188 μm, a thermal shrinkage of 0.26% in the MD direction, and a thermal shrinkage of 0% in the TD direction was used. As the protective film substrate, a thickness of 55 μm and the MD direction was used. Except for the PET film having a thermal shrinkage of 0.5% and a thermal shrinkage of 0.08% in the TD direction, a transparent conductive film with a protective film was produced in the same manner as in Example 1 and evaluated. The obtained results are shown in Table 1.

[Example 5]

In Example 5, as a transparent plastic film substrate, a PET film having a thickness of 188 μm, a thermal shrinkage of 0.26% in the MD direction, and a thermal shrinkage of 0% in the TD direction was used. As the protective film substrate, a thickness of 135 μm and the MD direction was used. Except for the PET film having a thermal shrinkage of 0.51% and a thermal shrinkage of 0.2% in the TD direction, a transparent conductive film with a protective film was produced in the same manner as in Example 1 and evaluated. Will get the result Shown in Table 1.

[Comparative Example 1]

In Comparative Example 1, as a transparent plastic film substrate, a PET film having a thickness of 60 μm, a thermal shrinkage rate of 0.74% in the MD direction, and a 0.46% thermal shrinkage rate of TD direction was used, and a protective film substrate was used with a thickness of 135 μm and MD direction. Except for a PET film having a thermal shrinkage of 0.06% and a thermal shrinkage of 0.03% in the TD direction, a transparent conductive film with a protective film was produced in the same manner as in Example 1 and evaluated. The obtained results are shown in Table 1.

[Comparative Example 2]

In Comparative Example 2, as a transparent plastic film substrate, a PET film having a thickness of 60 μm, a thermal shrinkage rate of 0.74% in the MD direction, and a 0.46% thermal shrinkage rate of TD direction was used. As a protective film substrate, a thickness of 135 μm and MD direction was used. Except for a PET film having a thermal shrinkage of 0.67% and a thermal shrinkage of 0.12% in the TD direction, a transparent conductive film with a protective film was produced in the same manner as in Example 1 and evaluated. The obtained results are shown in Table 1.

[Comparative Example 3]

In Comparative Example 3, a PET film having a thickness of 135 μm, a thermal shrinkage of 0.67% in the MD direction, and a thermal shrinkage of 0.12% in the TD direction was used as a protective film substrate. A tape was produced in the same manner as in Example 1. A protective conductive transparent conductive film was evaluated. The obtained results are shown in Table 1.

[Comparative Example 4]

In Comparative Example 4, a transparent conductive film with a protective film was produced in the same manner as in Example 1 except that a hard coat layer was provided only on the transparent conductive film side of the transparent plastic film substrate and not on the protective film substrate side. Film and evaluated. The obtained results are shown in Table 1.

Industrial availability

As described above in detail, according to the present invention, in a transparent conductive film with a protective film, hard coatings are provided on both sides of a transparent plastic film substrate, and the transparent plastic film substrate and the protective film substrate are set in a predetermined state. The thermal shrinkage rate in the MD direction under the conditions is a value within a respective predetermined range, so that the occurrence of curl can be effectively suppressed even when the annealing treatment is performed.

As a result, according to the present invention, it is possible to obtain a product which is excellent in operability and can effectively suppress the occurrence of curl even when an annealing treatment is performed. Transparent conductive film with protective film.

Therefore, the transparent conductive film of the present invention can be expected to contribute significantly to the improvement of the quality of display devices such as liquid crystal displays.

Claims (8)

A transparent conductive film with a protective film includes a transparent conductive film with a protective film, which is formed by sequentially stacking a transparent conductive film, a first hard coating layer, a transparent plastic film substrate, a second hard coating layer, and a protective film. The protective film is composed of an adhesive layer and a protective film substrate, and is releasably laminated on the second hard coating layer; wherein the first hard coating layer and the second hard coating layer, or any one of them It consists of a cured product of the active energy ray curable resin composition, and the weight ratio of the polymerizable compound A to the polymerizable compound B in the active energy ray curable resin composition (that is, the polymerizable compound A / the polymerizable compound B) is a value in the range of 15/85 to 85/15, in which the polymerizable compound A has two or more groups represented by the following general formula (1) in one molecule and is other than the group The rest of the structure does not contain an alkylene oxide unit, and the polymerizable compound B has three or more groups represented by the following general formula (2) in one molecule; and the transparent plastic film substrate is heated at 150 ° C. for 60 minutes. The thermal shrinkage ratio in the MD direction at the time is a value of 0.6% or less, The thermal shrinkage of the protective film substrate in the MD direction when heated at 150 ° C for 60 minutes is a value of 0.6% or less, In the general formula (1), R is an independent hydrogen atom or a methyl group, and * represents a bonding portion, In the general formula (2), R ¹ is an independent hydrogen atom or a methyl group, A is an independent alkylene group having 1 to 5 carbon atoms, the repeating number n is an independent integer of 1 or more, and * represents a bonding portion. . The transparent conductive film with a protective film according to the first patent application scope, wherein the transparent plastic film substrate has a thermal shrinkage in the MD direction when heated at 150 ° C for 60 minutes, and the protective film substrate is heated at 150 ° C. The difference in the heat shrinkage rate in the MD direction at 60 minutes is a value in the range of -0.5 to 0.5%. The transparent conductive film with a protective film according to item 1 of the scope of the patent application, wherein the transparent plastic film substrate has a thermal shrinkage rate of 0.6% or less in the TD direction when heated at 150 ° C. for 60 minutes. The thermal shrinkage rate of the protective film substrate in the TD direction when heated at 150 ° C. for 60 minutes is a value of 0.6% or less. The transparent conductive film with a protective film according to item 1 of the scope of patent application, wherein the transparent conductive film with a protective film is cut out into a square of 100 mm in the MD direction and 100 mm in the TD direction, and the protective film side is The absolute value of the curl value when the lower side was heated at 150 ° C. for 60 minutes was a value of 25 mm or less. The transparent conductive film with a protective film according to item 1 of the scope of patent application, wherein the thickness of the first hard coating layer and the second hard coating layer is a value in a range of 1 to 15 μm . The transparent conductive film with a protective film according to item 1 of the scope of patent application, wherein the thickness of the protective film substrate is a value in the range of 10 to 300 μm . The transparent conductive film with a protective film according to item 1 of the scope of the patent application, wherein the thickness of the transparent plastic film substrate is a value in a range of 10 to 200 μm . The transparent conductive film with a protective film according to item 1 of the scope of patent application, wherein an optical adjustment layer is provided between the first hard coat layer and the transparent conductive film.