JP6227321B2 - Transparent conductive film with protective film - Google Patents

Description

The present invention relates to a transparent conductive film with a protective film.
In particular, the present invention relates to a transparent conductive film with a protective film that is excellent in handling properties and can effectively suppress the occurrence of curling even when annealing is performed.

2. Description of the Related Art Conventionally, a touch panel that can input information by directly touching an image display unit has a light transmissive input device arranged on a display.
As a typical form of such a touch panel, a resistive film type touch panel in which two transparent electrode substrates are arranged with a gap so that the transparent electrode layers face each other, or between a transparent electrode film and a finger is generated. There is a capacitive touch panel that utilizes a change in capacitance.

Among these, in the capacitive touch panel, a transparent conductive film formed by laminating a transparent conductive film on a transparent plastic film substrate is widely used as a film sensor for detecting the touch position of a finger.
In addition, in order to improve the electrical conductivity of the transparent conductive film in the transparent conductive film, a process of crystallizing the transparent conductive film laminated on the transparent plastic film by a heat treatment, a so-called annealing process is performed. Widely implemented.

In addition, with the demand for thinning a smartphone or the like equipped with a capacitive touch panel, the transparent conductive film is also required to be thinned.
On the other hand, for transparent conductive films, a high degree of durability is required due to the use application as a touch panel, and from the viewpoint of precisely forming a patterned transparent conductive film, strict dimensions are required. Stability is also required.

Therefore, in order to meet these requirements, a hard coat film having a hard coat layer on the surface of a transparent plastic film substrate has been disclosed (for example, see Patent Document 1).
That is, Patent Document 1 is a hard coat film having a hard coat layer on one side of a plastic substrate film (transparent plastic film substrate), which satisfies the following requirements (1) to (5). A hard coat film is disclosed.
(1) The thickness of the plastic substrate film is 50 μm or more and 500 μm or less (2) The film thickness of the hard coat layer is 1 μm or more and 30 μm or less (3) The pencil hardness of the hard coat film is H or more (4) 150 ° C., 30 minutes treatment Thermal shrinkage after 0.1% or more and 2% or less (5) Curl value after treatment at 150 ° C. for 30 minutes measured by the following measurement method is 0 mm or more and 5 mm or less (measurement method)
Two film samples are cut out in a size of 20 cm in the vertical direction, 2 cm in the width direction, 2 cm in the vertical direction, and 20 cm in the width direction, and left for 30 minutes in a hot air circulation oven at 150 ° C. for heat treatment. It was. After leaving to cool at room temperature, the plastic substrate film surface was placed on a glass plate, and the amount of lifting at the four corners in the vertical direction from the glass plate surface was measured. In the two cut film samples, the maximum lifting amount was taken as the curl value.

JP 2011-31457 A (Claims)

  However, since the hard coat film disclosed in Patent Document 1 is characterized by having a hard coat layer only on one side of the transparent plastic film substrate, when the annealing treatment is performed, There was a problem that it was difficult to reliably suppress the occurrence of curling due to the difference between the heat shrinkage rate and the heat shrinkage rate of the transparent plastic film substrate.

In addition, in order to compensate for the handling properties that have been lowered due to the thinning, recent transparent conductive films can be peeled off from the surface of the transparent plastic film substrate opposite to the side on which the transparent conductive film is formed. A method is employed in which a protective film is laminated in an auxiliary manner and finally peeled off.
In this regard, in the case of the hard coat film disclosed in Patent Document 1, even if the occurrence of curl can be suppressed to some extent in the case of the hard coat film alone, Due to the difference between the heat shrinkage rate of the film and the heat shrinkage rate of the protective film, there was a problem that the curl was remarkably generated.

Therefore, the present inventors made extensive efforts in view of the above circumstances, and provided hard coat layers on both sides of the transparent plastic film substrate, as well as predetermined conditions in the transparent plastic film substrate and the protective film substrate. The present invention has been completed by finding that curling can be effectively suppressed even when annealing is performed by setting the thermal shrinkage in the MD direction within a predetermined range. It is.
That is, an object of the present invention is to provide a transparent conductive film with a protective film that can effectively suppress the occurrence of curling even when it is annealed while being excellent in handling properties. is there.

According to the present invention, a transparent conductive film with a protective film comprising a transparent conductive film, a first hard coat layer, a transparent plastic film substrate, a second hard coat layer, and a protective film, which are sequentially laminated. A protective film comprising a pressure-sensitive adhesive layer and a protective film base material, and is peelably laminated to the second hard coat layer. The first hard coat layer and the first hard coat layer The hard coat layer 2 or any one of them is made of a cured product of the active energy ray-curable resin composition, and two or more of the following general formulas (1) per molecule in the active energy ray-curable resin composition (1 A polymerizable compound (A) having a group represented by formula (1) and not containing an alkylene oxide unit in the remaining structure excluding the group; The weight ratio (polymerizable compound (A) / polymerizable compound (B)) of 5 to 8 polymerizable compounds (B) having a group represented by the following general formula (2) is 15/85 to 85. / 15, and the thermal shrinkage in the MD direction when heated at 150 ° C. for 60 minutes in a transparent plastic film substrate is set to a value of 0.6% or less, and 150 ° C. in the protective film substrate. A transparent conductive film with a protective film, characterized in that the heat shrinkage rate in the MD direction when heated for 60 minutes at a value of 0.6% or less, is provided, and the above-described problems can be solved.

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

(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 * indicates a bonding part. )

That is, since the transparent conductive film with a protective film of the present invention is supported by the protective film, excellent handling properties can be imparted to the thinned transparent conductive film.
In the case of the transparent conductive film with a protective film of the present invention, hard coat layers are provided on both surfaces of the transparent plastic film substrate, and heat in the MD direction under predetermined conditions on the transparent plastic film substrate and the protective film substrate is provided. Since the shrinkage rate is set to a value within a predetermined range, the occurrence of curling can be effectively suppressed even when annealing is performed.
Furthermore, in the case of the transparent conductive film with a protective film of the present invention, since the hard coat layer is provided on both surfaces of the transparent plastic film substrate, the occurrence of curling in the transparent conductive film alone after the protective film is peeled off Can also be effectively suppressed.
In addition, MD direction means the elongate direction at the time of film shaping, and TD direction means the width direction at the time of film shaping.
  Moreover, the transparent conductive film with a protective film of this invention means both the thing before annealing treatment and the thing after annealing treatment.
Moreover, by comprising in this way, while providing suitable surface hardening to the hard-coat layer obtained, the distortion | strain resulting from heat contraction can be disperse | distributed and relieve | moderated.

Further, in constituting the transparent conductive film with a protective film of the present invention, the heat shrinkage rate in the MD direction when heated at 150 ° C. for 60 minutes in the transparent plastic film base material, and the protective film base material at 150 ° C. for 60 minutes. It is preferable to set the difference between the heat shrinkage rate in the MD direction when heated to a value within the range of -0.5 to 0.5%.
With this configuration, even when annealing is performed, the occurrence of curling can be more effectively suppressed.

Further, in constituting the transparent conductive film with a protective film of the present invention, the heat shrinkage rate in the TD direction when heated at 150 ° C. for 60 minutes in the transparent plastic film substrate is set to a value of 0.6% or less. It is preferable that the thermal shrinkage rate in the TD direction when heated at 150 ° C. for 60 minutes in the substrate is set to a value of 0.6% or less.
With this configuration, even when annealing is performed, the occurrence of curling can be more effectively suppressed.

Further, in constructing the transparent conductive film with a protective film of the present invention, the transparent conductive film with a protective film is cut into a square of 100 mm in the MD direction and 100 mm in the TD direction, and the protective film side is on the lower side. The absolute value of the curl value when heated for a minute is preferably set to a value of 25 mm or less.
With this configuration, even when annealing is performed, the occurrence of curling can be more effectively suppressed.

Moreover, when comprising the transparent conductive film with a protective film of this invention, it is preferable to make the thickness of a 1st hard-coat layer and a 2nd hard-coat layer into the value within the range of 1-15 micrometers.
By comprising in this way, generation | occurrence | production of the curl resulting from the heat shrink of a transparent plastic film base material can be suppressed, and the outgas generation | occurrence | production at the time of the annealing process resulting from a hard-coat layer can also be suppressed.

Moreover, when comprising the transparent conductive film with a protective film of this invention, it is preferable to make the thickness of a protective film base material into the value within the range of 10-300 micrometers.
By comprising in this way, generation | occurrence | production of the curl at the time of the annealing process of a transparent conductive film can be suppressed, and the curl of protect film base material itself can also be suppressed.

Moreover, when comprising the transparent conductive film with a protective film of this invention, it is preferable to make the thickness of a transparent plastic film base material into the value within the range of 10-200 micrometers.
By comprising in this way, while making the uniformity of the thickness of a hard-coat layer or a transparent conductive film excellent, etc., the outgas generation resulting from a transparent plastic film base material can be suppressed.

Moreover, when comprising 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 this configuration, when the transparent conductive film is formed into a pattern shape by etching treatment, the visibility does not differ between the existing portion and the non-existing portion of the transparent conductive film (the pattern shape is difficult to visually recognize). Can be adjusted).

Fig.1 (a)-(b) is a figure provided in order to demonstrate the transparent conductive film with a protective film of this invention. FIG. 2 is a diagram for explaining the relationship between the thermal shrinkage rate in the MD direction in the transparent plastic film substrate and the curl value in the transparent conductive film with a protective film. FIG. 3 is a diagram provided to explain the relationship between the thermal shrinkage rate in the MD direction of the protect film substrate and the curl value of the transparent conductive film with the protect film. FIG. 4 is a diagram provided to explain the relationship between the difference in thermal shrinkage in the MD direction between the transparent plastic film substrate and the protect film substrate and the curl value of the transparent conductive film with the protect film.

As shown in FIG. 1 (a), the first embodiment of the present invention includes a transparent conductive film 1, a first hard coat layer 2a, a transparent plastic film substrate 3, and a second hard coat layer. 2b and a transparent conductive film 10 with a protective film in which a protective film 7 is laminated in order, and the protective film 7 is composed of an adhesive layer 4 and a protective film substrate 5, and a second hard It is laminated so as to be peelable with respect to the coat layer 2b, and the heat shrinkage rate in the MD direction when heated at 150 ° C. for 60 minutes in the transparent plastic film substrate 3 is set to a value of 0.6% or less to protect. Transparent conductivity with a protective film, characterized in that the heat shrinkage rate in the MD direction when heated at 150 ° C. for 60 minutes in the film substrate 5 is set to a value of 0.6% or less Is Irumu.
Embodiments of the present invention will be specifically described below with reference to the drawings as appropriate.

1. Types of transparent plastic film substrate (1) The resin used for the transparent plastic film substrate is not particularly limited as long as it is excellent in flexibility and transparency. Polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate Polyester film such as phthalate, polycarbonate film, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate Copolymer film, polystyrene film, polymethylpentene film, polysulfone film, polyetheretherketone Examples thereof include plastic films such as films, polyethersulfone films, polyetherimide films, polyimide films, fluororesin films, polyamide films, acrylic resin films, polyurethane resin films, norbornene resin films, and cycloolefin resin films.
Among these, since it is excellent in transparency and has versatility, it is preferable to use a transparent resin film made of polyethylene terephthalate or polycarbonate.

(2) Thermal contraction rate In this invention, the thermal contraction rate of MD direction at the time of heating at 150 degreeC for 60 minutes in a transparent plastic film base material is made into the value of 0.6% or less.
The reason for this is that, together with the predetermined heat shrinkage characteristics of the protective film substrate described later, even when the annealing treatment is performed in the state of the transparent conductive film with the protective film, the curling is effectively suppressed. It is because it can do.
In other words, when the MD thermal contraction rate of the transparent plastic film substrate exceeds 0.6%, the curl is effectively generated regardless of the difference in the MD thermal contraction rate of the protective film substrate. This is because it may be difficult to suppress it. On the other hand, the lower limit value of the thermal shrinkage rate in the MD direction in the transparent plastic film substrate includes 0%. However, in order to set the lower limit value to an excessively small value, it is necessary to add fine particles or the like, or to blend a material having excellent heat resistance, which may deteriorate the optical characteristics.
Therefore, it is more preferable to set the thermal shrinkage rate in the MD direction when heated at 150 ° C. for 60 minutes in the transparent plastic film substrate to a value within the range of 0.01 to 0.5%, and 0.05 to 0.00. More preferably, the value is within the range of 3%.
In addition, the interaction between the predetermined heat shrinkage characteristic in the transparent plastic film base material and the predetermined heat shrinkage characteristic in the protect film base material is the MD direction in the transparent plastic film base material. And are bonded so that the MD direction in the protective film substrate matches.
In order to make the heat shrinkage rate of the transparent plastic film substrate within the above-mentioned range, it is basically easiest to select such a transparent plastic film substrate. The heat shrinkage treatment is performed at a temperature, and the heat shrinkage rate can be adjusted by performing a relaxation treatment in the MD direction at that time (the heat shrinkage rate in the TD direction and the heat shrinkage rate in the protective film substrate to be described later) The same).

Here, the relationship between the thermal shrinkage rate in the MD direction in the transparent plastic film substrate and the curl value in the transparent conductive film with a protective film will be described with reference to FIG.
That is, in FIG. 2, the horizontal axis represents the thermal shrinkage rate (%) in the MD direction when heated at 150 ° C. for 60 minutes in the transparent plastic film substrate, and the vertical axis represents the curl value of the transparent conductive film with a protective film. A scatter diagram with (mm) taken is shown.
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 is cut into a square of 100 mm in MD direction and 100 mm in TD direction as a test piece, and the test piece is left to stand for 60 minutes in a furnace at a temperature of 150 ° C. with the protective film side down. Put.
Next, the test piece is left to stand on a glass plate for 60 minutes in an environment of a temperature of 23 ° C. and a humidity of 50% RH with the protective film side facing down.
And the amount of lifting of the four corners of the test piece in the vertical direction from the glass plate surface is measured with a caliper, and the maximum value among the obtained amounts of lifting is taken as the curl value.
If the four corners do not float from the glass plate surface and the central part of the film floats, turn the front and back of the transparent conductive film with a protective film and measure the amount of lift at the four corners. A minus value is added to the maximum value of to obtain a curl value.
Moreover, what was produced as Examples 1-5 and the comparative example 1 mentioned later were used for the transparent conductive film with a protective film as a measuring object.
That is, a transparent conductive film with a protective film whose thermal shrinkage rate in the MD direction in the protective film substrate was a value of 0.6% or less was measured.

As understood from the scatter diagram, under the condition that the thermal shrinkage rate in the MD direction in the protective film base material is 0.6% or less, the thermal shrinkage rate in the MD direction in the transparent plastic film base material is 0.6. If the value is less than or equal to%, the curl value can be suppressed to an allowable range of about -20 to 20 mm.
On the other hand, even when the thermal shrinkage rate in the MD direction in the protective film substrate is a value of 0.6% or less, the thermal shrinkage rate in the MD direction in the transparent plastic film substrate exceeds 0.6%. As a result, the curl value becomes less than −40 mm or exceeds 40 mm, and it is practically impossible to suppress to an allowable range, which causes a problem.
Therefore, from the scatter diagram shown in FIG. 2, from the viewpoint of effectively suppressing the occurrence of curling in the transparent conductive film with a protective film, the thermal shrinkage rate in the MD direction of the protective film substrate is a value of 0.6% or less. Under the conditions, it is understood that the heat shrinkage rate in the MD direction in the transparent plastic film substrate needs to be a value of 0.6% or less.

Moreover, it is preferable to make the thermal contraction rate of the TD direction at the time of heating for 60 minutes at 150 degreeC in a transparent plastic film base material into the value of 0.6% or less.
The reason for this is that the thermal contraction rate in the TD direction of the transparent plastic film substrate is set to a value within this range, so that the occurrence of curling can be more effectively suppressed even when annealing is performed. This is because it can.
That is, when the thermal shrinkage rate in the TD direction exceeds 0.6%, it is difficult to effectively suppress the occurrence of curl regardless of the difference from the thermal shrinkage rate in the TD direction in the protective film substrate. This is because it may become.
Therefore, it is more preferable to set the thermal shrinkage rate in the TD direction when heated at 150 ° C. for 60 minutes in the transparent plastic film substrate to a value of 0.5% or less, and further to a value of 0.3% or less preferable.

(3) Thickness Moreover, it is preferable to make the thickness of a transparent plastic film base material into the value within the range of 10-200 micrometers.
The reason for this is that by setting the thickness of the transparent plastic film substrate within such a range, the coating property of the hard coat layer and the subsequent lamination property of the transparent conductive film are excellent, and the transparent plastic film It is because generation | occurrence | production of the outgas resulting from a film base material can be suppressed.
That is, when the thickness of the transparent plastic film substrate is less than 10 μm, thickness unevenness may occur when the hard coat layer and the transparent conductive film are laminated. On the other hand, if the thickness of the transparent plastic film substrate exceeds 200 μm, outgassing during annealing may be a problem.
Accordingly, the thickness of the transparent plastic film substrate is more preferably set to a value within the range of 30 to 150 μm, and further preferably set to a value within the range of 50 to 100 μm.

2. Hard Coat Layer The present invention is characterized in that a first hard coat layer is provided on one surface of a transparent plastic film substrate and a second hard coat layer is provided on the other surface.
The first hard coat layer and the second hard coat layer may be made of different material materials or may have different thicknesses, but the transparent conductive film after the protective film is peeled off From the viewpoint of effectively suppressing the occurrence of curling in a single body, it is preferable that the curls are made of the same material and have the same thickness.
Therefore, in the following description, the first hard coat layer and the second hard coat layer will be described without distinction.

(1) Material substance The hard-coat layer which concerns on this embodiment is a layer containing the hardened | cured material of active energy ray curable resin. The content of the cured product of the active energy ray-curable resin in the layer is preferably 70 to 100% by weight, more preferably 80 to 100% by weight, and still more preferably 90 to 90% by weight with respect to the total weight of the hard coat layer. 100% by weight.

  As this active energy ray curable resin (hereinafter sometimes abbreviated as curable resin), those that can be used for conventional hard coat layers can be used freely. Furthermore, from the viewpoint of most exerting the effect of suppressing curling that occurs during the annealing treatment, the curable resin has two or more groups represented by the general formula (1) in one molecule, and A polymerizable compound (A) that does not contain an alkylene oxide unit in the remaining structure excluding the group, and a polymerizable compound (B) having three or more groups represented by the above general formula (2) in one molecule ) And a photopolymerization initiator (C).

(I) Polymerizable compound (A) (hereinafter sometimes referred to as component (A))
The curable resin has two or more groups represented by the following general formula (1) in one molecule, and a polymerizable compound containing no alkylene oxide unit in the remaining structure excluding the group ( It is preferable to contain A). By containing the polymerizable compound (A), the surface hardness of the obtained hard coat layer can be increased.

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

The number of groups represented by the general formula (1) in one molecule of the polymerizable compound (A) is 2 or more, preferably 2 to 16, more preferably 2 to 12, and still more preferably. Is from 3 to 10, more preferably from 3 to 8.
When the number of the groups is less than 2, a sufficient cross-linked structure is not formed, and the surface hardness of the obtained hard coat layer is lowered, so that the support function of the transparent plastic film substrate by the hard coat layer is not sufficient. In some cases, curling due to thermal shrinkage of the transparent plastic film substrate during the annealing treatment cannot be suppressed. On the other hand, when the number exceeds 16, the crosslink density becomes too high, the flexibility of the resulting hard coat layer is lost, and the strain generated during annealing cannot be dispersed or alleviated. Curling may occur due to differences.

  The polymerizable compound (A) is a compound that does not contain an alkylene oxide unit in the remaining structure excluding the group represented by the general formula (1). A compound containing an alkylene oxide unit has a long chain length of an alkylene oxide structure, so that the distance between cross-linking points is increased, and the structure of the entire hard coat layer tends to be sparse, resulting in the surface hardness of the hard coat layer. It is thought to cause a decrease in Therefore, in the present invention, it is considered that the surface hardness of the obtained hard coat layer is increased by using such a polymerizable compound as the component (A).

Examples of such a polymerizable compound (A) include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipenta. Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin 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 di (meth) acrylate, and two or more groups represented by the above general formula (1) in the molecule, The Examples include oligoester (meth) acrylates, oligoether (meth) acrylates, oligourethane (meth) acrylates, oligoepoxy (meth) acrylates and the like that do not contain an alkylene oxide unit in the remaining structure excluding .
In addition, you may use these (A) component individually or in combination of 2 or more types.

(Ii) Polymerizable compound (B) (hereinafter sometimes referred to as component (B))
The curable resin used in the present invention preferably contains three or more polymerizable compounds (B) having a group represented by the following general formula (2) in one molecule.
A polymerizable compound (B) having 3 or more groups per molecule in which a (meth) acryloyl group and an alkylene oxide chain directly represented by the general formula (2) are combined is contained together with the component (A). Thus, the obtained hard coat layer can have both a rigid part derived from the component (A) and a flexible part derived from the component (B), and the rigid part suppresses thermal shrinkage of the transparent plastic film substrate. It is considered that the flexible part can relieve / disappear the strain accompanying thermal shrinkage, thereby effectively suppressing the curling of the transparent conductive film due to the annealing treatment.
The component (B) also has an effect of imparting an appropriate polarity to the hard coat layer surface. That is, the hard coat layer having the component (A) and the component (B) does not cause repelling of the coating liquid even when a nano-order coating film such as an optical adjustment layer described later is formed. It is possible to prevent the occurrence of defects in the optical adjustment layer.

In the general formula (2), R ¹ independently represents a hydrogen atom or a methyl group. In addition, * shows a coupling | bond part. A independently represents an alkylene group having 1 to 5 carbon atoms, preferably an ethylene group or a propylene group, and more preferably an ethylene group. When A is the alkylene group, the obtained hard coat layer can have appropriate flexibility, and strain generated in the transparent plastic film substrate or the hard coat layer during the annealing treatment can be reduced or eliminated.

  In addition, the content of the ethylene oxide unit with respect to all the alkylene oxide units contained in one molecule of the polymerizable compound (B) is the adhesiveness to the laminated transparent conductive film and the optical adjustment layer described later, and the adhesive. From the viewpoint of improving the adhesiveness, it is preferably 60 to 100 mol%, more preferably 75 to 100 mol%, still more preferably 85 to 100 mol%, and most preferably substantially 100 mol%.

n represents the number of alkylene oxide units, and each independently represents an integer of 1 or more.
Moreover, in one molecule of the polymerizable compound (B), the total value of n in the general formula (2) (the total number of alkylene oxide units in one molecule of the polymerizable compound (B)) is 3 or more. However, Preferably it is 4-20, More preferably, it is 6-16, More preferably, it is 8-14.
If the said total value is 4 or more, the softness | flexibility is provided to the hard-coat layer obtained, and the effect which relieve | moderates and lose | disappears the distortion | strain at the time of annealing treatment can be anticipated.
On the other hand, when the said total value exceeds 20, the rigidity of a hard-coat layer may become inadequate and the effect which suppresses the heat shrink of a transparent plastic film base material may become inadequate.

The number of groups represented by the general formula (2) in one molecule of the polymerizable compound (B) is 3 or more, preferably 3 to 16, more preferably 3 to 12, and still more preferably. Is 3 to 10, more preferably 5 to 8.
When the number of the groups is less than 3, the crosslink density of the obtained hard coat layer is lowered, and the surface hardness is lowered, which is not preferable.
On the other hand, if it is 16 or less, since the fall of the softness | flexibility by a crosslinking density becoming high too much can be suppressed, it is preferable.

Examples of such a polymerizable compound (B) include alkylene oxide-modified glycerin tri (meth) acrylate, alkylene oxide-modified dipentaerythritol tetra (meth) acrylate, alkylene oxide-modified dipentaerythritol hexa (meth) acrylate, and the like. It is done.
In addition, you may use these (B) components individually or in combination of 2 or more types.

In the curable resin, the weight ratio ((A) / (B)) between the component (A) and the component (B) is 15/85 to 85/15, preferably 20/80 to 80/20, More preferably, it is 28 / 72-72 / 28, More preferably, it is 35 / 65-65 / 35, More preferably, it is 41 / 59-59 / 41, More preferably, it is 46 / 54-54 / 46.
When the weight ratio is less than 15/85, the amount of the component (B) is too large, so that the surface hardness of the obtained hard coat layer is lowered, which is not preferable.
On the other hand, when the weight ratio exceeds 85/15, since the amount of the component (A) is too large, it is conceivable that the ability to eliminate strain due to heat of the obtained hard coat layer is lowered.

(Iii) Photopolymerization initiator (C) (hereinafter sometimes referred to as component (C))
Moreover, it is also preferable to contain a photoinitiator (C) depending on necessity from the viewpoint of efficiently curing the active energy ray-curable resin.
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, and 2,2-dimethoxy-2. -Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-die Tylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate and the like.
In addition, these may be used individually by 1 type and may be used in combination of 2 or more type.
Further, the blending amount of the photopolymerization initiator (C) is preferably set to a value within the range of 0.2 to 10 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B). More preferably, the value is in the range of 1 to 5 parts by weight.

(2) Composition for forming a hard coat layer Further, the hard coat layer is preferably formed by preparing a composition for forming a hard coat layer in advance, applying and drying as described below, and then curing. .
If necessary, the composition can be prepared by adding an active energy ray-curable resin and various additive components used as required in a suitable solvent at a predetermined ratio and dissolving or dispersing them.
Various additive components include, for example, silica fine particles, antioxidants, ultraviolet absorbers, (near) infrared absorbers, silane coupling agents, light stabilizers, leveling agents, refractive index adjusters, antistatic agents, extinguishing agents. A foaming agent etc. are mentioned.

Examples of the solvent used include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol, and butanol. Examples thereof include ketones such as alcohol, acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, and cellosolv solvents such as ethyl cellosolve.
The concentration and viscosity of the composition for forming a hard coat layer thus prepared may be within a range that can be coated, and can be appropriately selected depending on the situation.
Therefore, it is usually preferable to dilute the solid content concentration to be a value within the range of 0.05 to 10% by weight from the viewpoint of easily adjusting the thickness of the obtained hard coat layer to a desired range, It is more preferable to dilute such that the value is within the range of 0.1 to 8% by weight.

(3) Thickness Moreover, it is preferable to make the thickness of a hard-coat layer into the value within the range of 1-15 micrometers.
The reason for this is that when the thickness of the hard coat layer is less than 1 μm, the holding function against heat shrinkage of the transparent plastic film substrate by the annealing treatment becomes insufficient, and curling may not be suppressed. .
On the other hand, when the thickness of the hard coat layer exceeds 15 μm, outgas may be generated from the hard coat layer due to the annealing treatment.
Therefore, the thickness of the hard coat layer is more preferably set to a value within the range of 1.5 to 10 μm, and further preferably set to a value within the range of 2 to 5 μm.

(4) Hardness Further, the pencil hardness measured according to JIS K 5600-5-4 of the hard coat layer is preferably in the range of 2B to 6H, more preferably in the range of HB to 5H. More preferably, it is within the range of H to 4H.

3. Transparent conductive film (1) Material substance The material substance of the transparent conductive film is not particularly limited as long as it has both transparency and conductivity. For example, indium oxide, zinc oxide, tin oxide , Indium tin oxide (ITO), tin antimony oxide, zinc aluminum oxide, indium zinc oxide, and the like.
In particular, it is preferable to use ITO as a material substance.
This is because if ITO is used, a transparent conductive film excellent in transparency and conductivity can be formed by employing appropriate film forming conditions.

(2) Thickness Moreover, it is preferable to make the thickness of a transparent conductive film into the value within the range of 5-500 nm.
This is because when the thickness of the transparent conductive film is less than 5 nm, the transparent conductive film becomes brittle and sufficient conductivity may not be obtained. On the other hand, when the thickness of the transparent conductive film exceeds 500 nm, the color attributed to the transparent conductive film becomes strong and the pattern shape of the transparent conductive film may be easily recognized.
Therefore, the thickness of the transparent conductive film is more preferably set to a value within the range of 15 to 250 nm, and further preferably set to a value within the range of 20 to 100 nm.

(3) Conductivity Further, the surface electrical resistance of the transparent conductive film after the annealing treatment is preferably set to a value within the range of 10 to 1000Ω / □, and set to a value within the range of 50 to 500Ω / □. More preferably, the value is more preferably in the range of 100 to 300 Ω / □.

4). Optical Adjustment Layer As the second embodiment, as shown in FIG. 1B, the transparent conductive film 1 and the first hard in the transparent conductive film 10 with a protective film according to the first embodiment described above. The structure which provides the optical adjustment layer 8 between the coat layers 2a is mentioned preferably. By providing the optical adjustment layer 8, 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 is not easily recognized. Because it can.

Here, as shown in FIG. 1B, the optical adjustment layer 8 is formed on the first hard coat layer 2a and the high refractive index layer 8a having a relatively high refractive index, and the refractive index is relatively low. It is preferable that the low refractive index layer 8b is sequentially laminated.
Hereinafter, the high refractive index layer 8a and the low refractive index layer 8b 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.
This is because when the refractive index of the high refractive index layer is less than 1.6, a significant refractive index difference from the low refractive index layer cannot be obtained, and the pattern shape of the transparent conductive film is easily visible. Because there is. On the other hand, if the refractive index of the high refractive index layer is 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 further 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.
This is because when the thickness of the high refractive index layer is less than 20 nm, the film of the high refractive index layer becomes fragile and the shape of the layer may not be maintained. On the other hand, when the thickness of the high refractive index layer exceeds 130 nm, the pattern shape of the transparent conductive film may be easily recognized.
Therefore, the thickness of the high refractive index layer is more preferably 23 to 120 nm, and further preferably 30 to 110 nm.

(1) -3 Material substance Moreover, it is preferable that a high refractive index layer consists of hardened | cured material of the composition containing metal oxide microparticles | fine-particles and an active energy ray hardening-type compound.
This is because the refractive index in the high refractive index layer can be easily adjusted by including the metal oxide fine particles.

(I) Metal oxide fine particles The types of metal oxides are tantalum oxide, zinc oxide, indium oxide, hafnium oxide, cerium oxide, tin oxide, niobium oxide, indium tin oxide (ITO), antimony tin oxide (ATO). Etc. are preferable.
Further, from the viewpoint of realizing a high refractive index without lowering transparency, it is particularly preferable that at least one selected from titanium oxide and zirconium oxide is used.
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 set to a value in the range of 0.005 μm to 1 μm. In addition, the average particle diameter of metal oxide fine particles can be calculated | required by the measuring method using the zeta potential measuring method, for example.
As a compounding quantity of metal oxide microparticles | fine-particles, it is preferable that it is 20-2000 weight part with respect to 100 weight part of below-mentioned active energy ray hardening-type compounds, It is more preferable that it is 80-1000 weight part, 150- More preferably, it is 400 parts by weight.

(Ii) Active energy ray-curable compound The active energy ray-curable compound used for forming the high refractive index layer is an electromagnetic wave or charged particle beam having energy quanta, that is, irradiation with ultraviolet rays or electron beams. This means a polymerizable compound that crosslinks and cures, and examples thereof include a photopolymerizable prepolymer and a photopolymerizable monomer.

  Further, the above-mentioned photopolymerizable prepolymer includes a radical polymerization type and a cationic polymerization type. Examples of the radical polymerization type photopolymerizable prepolymer include polyester acrylate, epoxy acrylate, urethane acrylate, polyol acrylate, and the like. Is mentioned.

Moreover, as a polyester acrylate type prepolymer, for example, by esterifying the hydroxyl group of a polyester oligomer having a hydroxyl group at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or The compound obtained by esterifying the terminal hydroxyl group of the oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth) acrylic acid.
Examples of the epoxy acrylate prepolymer include compounds obtained by esterifying an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin with (meth) acrylic acid.
Moreover, as a urethane acrylate type prepolymer, the compound obtained by esterifying the polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol, and polyisocyanate with (meth) acrylic acid is mentioned, for example.
Furthermore, as a polyol acrylate type prepolymer, the compound obtained by esterifying the hydroxyl group of polyether polyol with (meth) acrylic acid is mentioned.
In addition, these polymeric 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 cationic polymerization type photopolymerizable prepolymer, an epoxy resin is usually used.
Examples of such epoxy resins are compounds obtained by epoxidizing polyhydric phenols such as bisphenol resins and novolak resins with epichlorohydrin, etc., and by oxidizing a linear olefin compound or a cyclic olefin compound with a peroxide or the like. Compounds and the like.

Examples of the photopolymerizable monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol di (meth). Acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphoric acid Di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified Polyfunctional acrylates such as dipentaerythritol hexa (meth) acrylate are exemplified.
In addition, these photopolymerizable monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

(Iii) Photopolymerization initiator From the viewpoint of efficiently curing the active energy ray-curable compound, it is also preferable to use a photopolymerization initiator in combination as desired.
Examples of such photopolymerization initiators include radical polymerization type photopolymerizable prepolymers and photopolymerizable monomers such as 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-phenylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) keto Benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate, and the like.

Examples of the photopolymerization initiator for the cationic polymerization type photopolymerizable prepolymer include oniums such as aromatic sulfonium ions, aromatic oxosulfonium ions, aromatic iodonium ions, tetrafluoroborate, hexafluorophosphate, hexa Examples thereof include compounds composed of anions such as fluoroantimonate and hexafluoroarsenate.
In addition, these may be used individually by 1 type and may be used in combination of 2 or more type.
Moreover, as a compounding quantity of a photoinitiator, it is preferable to set it as the value within the range of 0.2-10 weight part with respect to 100 weight part of active energy ray hardening-type compounds mentioned above, 1-5 weight part It is more preferable to set the value within the range.

(1) -4 Composition for forming a high refractive index layer A high refractive index layer is prepared by preparing a composition for forming a high refractive index layer in advance, applying and drying it as described below, and then curing. It is preferable.
The composition is prepared by adding an active energy ray-curable compound, a photopolymerization initiator, and various additive components used as required in a suitable solvent, if necessary, and dissolving or dispersing them. can do.
Examples of various additive components include antioxidants, ultraviolet absorbers, (near) infrared absorbers, silane coupling agents, light stabilizers, leveling agents, antistatic agents, and antifoaming agents.

Examples of the solvent used include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol, and butanol. Examples thereof include ketones such as alcohol, acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, and cellosolv solvents such as ethyl cellosolve.
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 coated, and can be appropriately selected according to the situation.
Therefore, usually, from the viewpoint of easily adjusting the film thickness of the obtained high refractive index layer to a predetermined range, it is preferable to dilute to a solid content concentration of 0.05 to 10% by weight, and 0.1 to 8% by weight. It is more preferable to dilute to become%.

(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.
This is because when 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, when the refractive index of the low refractive index layer is 1.6 or more, a significant refractive index difference from the high refractive index layer cannot be obtained, and the pattern shape of the transparent conductive film may be easily visually recognized. Because.
Therefore, the refractive index of the low refractive index layer is more preferably 1.3 or more and less than 1.5, and further 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.
This is because when the thickness of the low refractive index layer is less than 10 nm, the film of the low refractive index layer becomes brittle and the shape of the layer may not be maintained. On the other hand, when the thickness of the low refractive index layer exceeds 150 nm, the pattern shape of the transparent conductive film may be easily visually recognized.
Therefore, the thickness of the low refractive index layer is more preferably 15 to 135 nm, and further preferably 20 to 120 nm.

(2) -3 Material substance Moreover, it is preferable that a low refractive index layer consists of hardened | cured material of the composition containing a silica fine particle and an active energy ray hardening-type compound.
This is because the refractive index in the low refractive index layer can be easily adjusted by including silica fine particles.

The silica fine particles are preferably hollow silica fine particles or porous silica fine particles.
This is because if the hollow silica fine particles or the porous silica fine particles are used, the refractive index of the low refractive index layer can be more effectively lowered to a predetermined range.
Furthermore, in order to exhibit the effect as a low refractive index layer, the average particle diameter of the silica fine particles is preferably 1 μm or less, and preferably within a range of 10 to 100 nm. The average particle diameter of the silica fine particles can be determined by, for example, a zeta potential measurement method.
Moreover, as a compounding quantity of a silica particle, it is preferable that it is 50-500 weight part with respect to 100 weight part of active energy ray hardening-type compounds mentioned above, It is more preferable that it is 80-300 weight part, 100- More preferably, it is 250 parts by weight.

(2) -4 Composition for forming a low refractive index layer The low refractive index layer is formed by preparing a composition for forming a low refractive index layer in advance, and applying and drying the composition as will be described later, followed by curing. It is preferable.
The composition is prepared by adding the above-mentioned silica fine particles, active energy ray-curable compound, photopolymerization initiator, and various additive components used as required in a suitable solvent at a predetermined ratio, respectively, It can be prepared by dispersing.
The various additive components, the solvent, the concentration of the composition for forming the low refractive index layer, the viscosity, and the like are the same as in the description of the high refractive index layer.

(3) Characteristics of optical adjustment layer In the second embodiment in which the optical adjustment layer is provided between the transparent conductive film and the first hard coat layer as described above, it is difficult to visually recognize the pattern-shaped transparent conductive film. Has the effect of Furthermore, 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 difficult to be visually recognized even after the annealing treatment.
More specifically, a normal transparent conductive film has a problem that even if an optical adjustment layer is provided, the pattern shape of the transparent conductive film becomes conspicuous after annealing. This is because the transparent conductive film portion made of an inorganic material has a small heat shrinkage rate, whereas the optical adjustment layer portion made of an organic material has a large heat shrinkage rate. It is thought that distortion occurs at the boundary of the nonexistent part.
On the other hand, in the transparent conductive film with a protective film of the present invention, curling is also suppressed in the direction of suppressing heat shrinkage of the transparent plastic film substrate. For this reason, in the second embodiment, the thermal shrinkage of the transparent plastic film substrate is suppressed, so that in the second embodiment, it is difficult to visually recognize the pattern shape of the transparent conductive film continuously after the annealing treatment. I can do it.
From the viewpoint of exerting such an effect, the thermal shrinkage rate in the MD direction and the TD direction of the transparent plastic film substrate is preferably 0.5% or less, and 0.3% or less. Is particularly preferred.
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. Protect Film (1) Protect Film Base (1) -1 Type The resin used for the protect film base can be improved in handling by laminating on a transparent conductive film. For example, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyolefin resins such as polypropylene, paper, and the like can be used.
Among these, polyester resins and polyolefin resins are more preferable.

(1) -2 Heat Shrinkage Rate In the present invention, the heat shrinkage rate in the MD direction when heated at 150 ° C. for 60 minutes in the protective film substrate is set to a value of 0.6% or less.
The reason for this is that, together with the predetermined heat shrinkage characteristics in the transparent plastic film substrate described above, even when the annealing treatment is performed in the state of the transparent conductive film with a protective film, the occurrence of curling is effectively suppressed. Because it can.
In other words, when the thermal shrinkage rate in the MD direction of the protective film base material exceeds 0.6%, curling is effectively generated regardless of the difference from the thermal shrinkage rate in the MD direction of the transparent plastic film base material. This is because it may be difficult to suppress it. On the other hand, in order to make the thermal shrinkage rate in the MD direction in the protective film base material too small, it is necessary to add fine particles or blend a material having excellent heat resistance. In some cases, outgassing is a problem during annealing.
Therefore, it is more preferable to set the thermal shrinkage rate in the MD direction when heated at 150 ° C. for 60 minutes in the protective film substrate to a value within the range of 0.01 to 0.6%, preferably 0.1 to 0.5. More preferably, the value is within the range of%.

Here, the relationship between the thermal shrinkage rate in the MD direction in the protective film substrate and the curl value in the transparent conductive film with the protective film will be described with reference to FIG.
That is, in FIG. 3, the horizontal axis represents the thermal shrinkage rate (%) in the MD direction when heated at 150 ° C. for 60 minutes in the protective film substrate, and the vertical axis represents the curl value of the transparent conductive film with the protective film ( mm) is shown.
In addition, what was produced as Examples 1-5 and Comparative Example 3 mentioned later were used for the transparent conductive film with a protective film as a measuring object.
That is, a transparent conductive film with a protective film whose thermal shrinkage rate in the MD direction in the transparent plastic film substrate was 0.6% or less was used as a measurement target.

As understood from the scatter diagram, under the condition that the thermal shrinkage rate in the MD direction in the transparent plastic film substrate is 0.6% or less, the thermal shrinkage rate in the MD direction in the protective film substrate is 0.6. If the value is less than or equal to%, the curl value can be suppressed to an allowable range of about -20 to 20 mm.
On the other hand, even when the thermal shrinkage rate in the MD direction in the transparent plastic film substrate is a value of 0.6% or less, the value in which the thermal shrinkage rate in the MD direction in the protective film substrate exceeds 0.6% As a result, the curl value becomes less than −40 mm or exceeds 40 mm, and it is practically impossible to suppress to an allowable range, which causes a problem.
Therefore, from the scatter diagram shown in FIG. 3, from the viewpoint of effectively suppressing the occurrence of curl in the transparent conductive film with a protective film, the value of the thermal shrinkage in the MD direction in the transparent plastic film substrate is 0.6% or less. Under these conditions, it is understood that the thermal contraction rate in the MD direction in the protective film substrate needs to be a value of 0.6% or less.
Further, considering both the scatter diagrams of FIG. 2 and FIG. 3, in order to effectively suppress the occurrence of curling in the transparent conductive film with a protective film, the thermal shrinkage rate in the MD direction of the transparent plastic film substrate is set to 0. It is understood that the heat shrinkage rate in the MD direction in the protective film base material needs to be 0.6% or less as well as a value of .6% or less.

Next, the relationship between the difference in thermal shrinkage in the MD direction between the transparent plastic film substrate and the protect film substrate and the curl value will be described with reference to FIG.
That is, in FIG. 4, the horizontal axis represents the difference (%) obtained by subtracting the thermal shrinkage rate (%) in the MD direction of the protective film base material from the thermal shrinkage rate (%) in the MD direction of the transparent plastic film base material. A scatter diagram in which the curl value (mm) in the transparent conductive film with a protective film is taken on the vertical axis is shown.
In addition, what was created as Examples 1-5 and Comparative Examples 1-3 mentioned later were used for the transparent conductive film with a protective film as a measuring object.

As understood from the scatter diagram, there is no clear correlation between the difference in the thermal shrinkage rate in the MD direction between the transparent plastic film substrate and the protective film substrate and the curl value.
More specifically, even if the absolute value of the difference in thermal shrinkage in the MD direction between the transparent plastic film substrate and the protect film substrate takes a relatively small value, the curl value may be a large value. On the contrary, it can be seen that even when the absolute value of the difference between the heat shrinkage rates is relatively large, the curl value may be small.
The reason for this is considered that when the difference in the thermal shrinkage rate in the MD direction is small and similar, the difference in the thermal shrinkage rate in the TD direction also affects.

However, when the thermal shrinkage rate in the MD direction in the transparent plastic film substrate is a value of 0.6% or less and the thermal shrinkage rate in the MD direction in the protection film substrate is a value of 0.6% or less. By setting these differences to values within a predetermined range, the occurrence of curling can be more effectively suppressed.
Therefore, the difference between the thermal shrinkage rate in the MD direction when heated at 150 ° C. for 60 minutes in the transparent plastic film substrate and the thermal shrinkage rate in the MD direction when heated at 150 ° C. for 60 minutes in the protective film substrate. A value within the range of −0.5 to 0.5% is preferable, a value within the range of −0.4 to 0.4% is more preferable, and −0.3 to 0.3%. It is more preferable to set the value within the range.

Moreover, it is preferable to make the thermal contraction rate of the TD direction at the time of heating at 150 degreeC for 60 minutes in a protect film base material into the value of 0.6% or less.
The reason for this is that by setting the thermal shrinkage rate in the TD direction of the protect film base to a value within such a range, the occurrence of curling can be more effectively suppressed even when annealing is performed. Because.
That is, when the thermal shrinkage rate in the TD direction exceeds 0.6%, curling can be effectively suppressed regardless of the difference from the thermal shrinkage rate in the TD direction in the transparent plastic film substrate. This is because it may be difficult. On the other hand, in order to make the thermal shrinkage rate in the TD direction in the protective film substrate too small, it is necessary to add fine particles or blend a material having excellent heat resistance. In some cases, outgassing is a problem during annealing.
Therefore, it is more preferable that the heat shrinkage rate in the TD direction when heated at 150 ° C. for 60 minutes in the protective film substrate is set to a value within the range of 0.01 to 0.5%, and 0.02 to 0.3. More preferably, the value is within the range of%.

(1) -3 Thickness It is also preferable to set the thickness of the protective film substrate to a value within the range of 10 to 300 μm.
The reason for this is that if the thickness of the protective film substrate is less than 10 μm, the effect of suppressing the curling of the transparent conductive film may be insufficient during the annealing treatment. On the other hand, when the thickness of the protective film substrate exceeds 300 μm, heat treatment is generated in the thickness direction on the protective film substrate itself after the annealing treatment, which may cause the protective film substrate itself to curl. Because there is.
Therefore, the thickness of the protective film substrate is more preferably set to a value within the range of 30 to 200 μm, and further preferably set to a value within the range of 50 to 150 μm.

(2) Pressure-sensitive adhesive layer (2) -1 Material substance The pressure-sensitive adhesive used for the pressure-sensitive adhesive layer is not particularly limited, and a conventionally known pressure-sensitive adhesive can be used.
For example, acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, polyvinyl ethers, vinyl acetate / vinyl chloride copolymers, modified polyolefins, epoxy polymers, fluorine polymers, natural rubber, synthetic rubber and other rubber polymers Can be appropriately selected and used.

(2) -2 Thickness Moreover, it is preferable to make the thickness of an adhesive layer into the value within the range of 2-50 micrometers.
This is because the adhesive strength may be insufficient when the thickness of the pressure-sensitive adhesive layer is less than 2 μm. On the other hand, when the thickness of the pressure-sensitive adhesive layer exceeds 100 μm, outgassing of the pressure-sensitive adhesive layer may cause a problem.
Therefore, the thickness of the pressure-sensitive adhesive layer is more preferably set to a value within the range of 5 to 50 μm, and further preferably set to a value within the range of 10 to 30 μm.

6). Curl value The transparent conductive film with a protective film of the present invention is cut into a square of 100 mm in MD direction × 100 mm in TD direction, and the absolute value of the curl value when heated at 150 ° C. for 60 minutes with the protective film side down. Is preferably set to a value of 25 mm or less.
The reason for this is that by setting the absolute value of the curl value measured by a predetermined method to a value within this range, curling can be more effectively suppressed even when annealing is performed. This is because it can.
That is, if the absolute value of the curl value exceeds 25 mm, there may be a problem in actual use.
The lower limit value of the absolute value of the curl value is 0 mm.
Therefore, it is more preferable that the absolute value of the curl value when cut into a square of 100 mm in the MD direction and 100 mm in the TD direction and heated at 150 ° C. for 60 minutes with the protect film side down is set to a value of 22 mm or less. More preferably, the value of
In the case where the optical adjustment layer is provided as described above, a change in the visibility of the pattern of the transparent conductive film after the annealing treatment can be effectively prevented as long as the absolute value of the curl value is in the above-described range. .

7). The manufacturing method of a transparent conductive film The transparent conductive film of this invention can be obtained with the manufacturing method containing the following process (a)-(g).
(A) A step of preparing a transparent plastic film base material having a heat shrinkage rate in the MD direction of 0.6% or less when heated at 150 ° C. for 60 minutes (b) First on one side of the transparent plastic film base material (C) forming a second hard coat layer on the other surface of the transparent plastic film substrate (d) forming a transparent conductive film on the first hard coat layer And (e) a step of preparing a protective film substrate having a thermal shrinkage in the MD direction of 0.6% or less when heated at 150 ° C. for 60 minutes. Step of forming a pressure-sensitive adhesive layer on one side of the substrate to obtain a protective film (g) Bonding with the pressure-sensitive adhesive layer in the protective film and the second hard coat layer in the transparent conductive film, Obtaining a film with a transparent conductive film or less, parts overlapping with the contents of the far omitted, will be described in detail, and only different parts.

(1) Process (a): The process of preparing a transparent plastic film base material The transparent plastic film base material whose heat shrinkage rate of MD direction at the time of heating for 60 minutes at 150 degreeC is a value of 0.6% or less is prepared. .
The details of the transparent plastic film substrate have already been described, and will be omitted.

(2) Step (b): Step of forming the first hard coat layer The above-described composition for forming the hard coat layer is applied to one side of the transparent plastic film substrate prepared in step (a) by a conventionally known method. After coating and forming a coating film, it is dried, and the first hard coat layer is formed by irradiating this with an active energy ray to cure the coating film.
Examples of the method for applying the composition for forming the hard coat layer include a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method.

Moreover, as drying conditions of a coating film, it is preferable to carry out for 10 second-about 10 minutes at 60-150 degreeC.
Furthermore, 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, a xenon lamp, and the like. The irradiation amount is usually preferably 100 to 500 mJ / cm ² .
On the other hand, examples of the electron beam light source include an electron beam accelerator, and the irradiation amount is preferably 150 to 350 kV.

(3) Step (c): Step of forming the second hard coat layer On the other surface of the transparent plastic film substrate prepared in step (a), in the same manner as the formation of the first hard coat layer, The composition for forming a hard coat layer is applied to form a coating film, and then dried, and the second hard coat layer is formed by irradiating the active energy ray to cure the coating film.

(4) Step (c ′): Step of Forming Optical Adjustment Layer If desired, a step of forming the optical adjustment layer can be provided as step (c ′) after step (c). The effects of providing the optical adjustment layer are as described above.
That is, on the surface of the first hard coat layer formed in the above-described step, the above-described composition for forming a high refractive index layer is applied by a conventionally known method to form a coating film, and then dried. A high refractive index layer is formed by irradiating an active energy ray to this and hardening a coating film.
Examples of the method for applying the composition for forming the high refractive index layer include a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method.

Moreover, as drying conditions, it is preferable to carry out at 60-150 degreeC for about 10 seconds-10 minutes.
Furthermore, 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, a xenon lamp, and the like. The irradiation amount is usually preferably 100 to 500 mJ / cm ² .
On the other hand, examples of the electron beam light source include an electron beam accelerator, and the irradiation amount is 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 applied and dried with the above-described composition for forming a low refractive index layer and irradiated with active energy rays in the same manner as the formation of the high refractive index layer on the hard coat layer 1. And can be cured.

(5) Step (d): Step of forming transparent conductive film Vacuum deposition method for the first hard coat layer (or the optical adjustment layer formed in step (c ′)) formed in step (b) A transparent conductive film is obtained by forming a transparent conductive film by a known method such as sputtering, CVD, ion plating, spraying or sol-gel.
Examples of the sputtering method include a normal sputtering method using a compound or a reactive sputtering method using a metal target.
At this time, it is also preferable to introduce oxygen, nitrogen, water vapor or the like as a reactive gas, or to use ozone addition or ion assist together.
In addition, after forming the transparent conductive film as described above, a resist mask having a predetermined pattern is formed by a photolithography method, and then an etching process is performed by a known method so that a line pattern or the like is formed. Can be formed.
As an etchant, an aqueous solution of an acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like is preferably used.

(6) Step (e): Step of preparing a protective film base material A protective film base material having a thermal shrinkage in the MD direction of 0.6% or less when heated at 150 ° C. for 60 minutes is prepared.
The details of the protective film base material have already been described, and will be omitted.

(7) Step (f): Step of forming the pressure-sensitive adhesive layer After applying the pressure-sensitive adhesive composition on one side of the protective film substrate prepared in step (e) to form a coating film by a conventionally known method , Dried or irradiated with active energy rays to form an adhesive layer to obtain a protective film.
Examples of the method for applying the pressure-sensitive adhesive composition include a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method.

(8) Step (g): bonding step The pressure-sensitive 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) are bonded. Then, a transparent conductive film with a protective film is obtained.
At this time, it bonds so that MD direction in a transparent conductive film and MD direction in a protective film base material may correspond.
In addition, as a bonding method, it can bond using a laminator, for example.

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

[Example 1]
1. Production of Transparent Conductive Film with Protective Film (1) Preparation of Transparent Plastic Film Base Material A transparent plastic film base material having a thickness of 60 μm, a thermal shrinkage rate of 0.26% in the MD direction, and a thermal shrinkage rate of 0% in the TD direction. A PET film was prepared.
Here, the thermal shrinkage rate of the transparent plastic film substrate was measured as follows.
That is, a square of 110 mm in the MD direction × 110 mm in the TD direction was cut out from the transparent plastic film substrate to obtain a test piece.
Next, a square of 100 mm in the MD direction × 100 mm in the TD direction was marked on the obtained test piece using a ballpoint pen.
Next, among the four sides of the square marked with a ballpoint pen, the length X (μm) of one side along the MD direction was measured using a digital micrometer (Model AT112, manufactured by Mitutoyo Corporation).
Subsequently, the test piece was left still for 60 minutes in a 150 degreeC hot-air circulation type oven.
After that, the test piece is taken out from the hot air circulation oven, and the length Y (μm) of one side along the MD direction is measured using the digital micrometer for the same side where the length is measured in the square marked with the ballpoint pen. Measured.
And the thermal contraction rate of MD direction was computed using the following formula (1).
Further, the thermal contraction rate in the TD direction was calculated in the same manner as the thermal contraction rate in the MD direction. (X−Y) / X × 100 = heat shrinkage rate (%) (1)

(2) Preparation of composition for forming hard coat layer 70 parts by weight (solid content) of pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “A-TMM-3L”) as the polymerizable compound (A) This represents the converted value. The same applies hereinafter.) 30 parts by weight of ethylene oxide-modified dipentaerythritol hexaacrylate (trade name “A-DPH-12E” manufactured by Shin-Nakamura Chemical Co., Ltd.) as the polymerizable compound (B), light As a polymerization initiator, 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Corporation, trade name “Irgacure 184”), and a siloxane-modified acrylic polymer leveling agent (manufactured by Big Chemie Japan Co., Ltd., trade name “BYK-”) 3550 ") 0.2 parts by weight was mixed to prepare an active energy ray curable resin, and then propylene glycol. Dilution with monomethyl ether gave a composition for forming a hard coat layer having a solid content of 30% by weight.

(3) Formation of Hard Coat Layer Next, a composition for forming a hard coat layer was applied to the surface of the prepared transparent plastic film substrate with a Mayer bar # 4.
Next, after drying in an oven at 70 ° C. for 1 minute, the surface of the transparent plastic film substrate was irradiated with UV light of 200 mJ / cm ² using a high-pressure mercury lamp in a nitrogen atmosphere, and the pencil hardness was H The first hard coat layer was formed.

Next, on the surface of the transparent plastic film substrate opposite to the side on which the first hard coat layer is formed, a hard coat layer forming composition similar to the first hard coat layer is applied at the Mayer bar # 4. Coated.
Next, after drying in an oven at 70 ° C. for 1 minute, the surface of the transparent plastic film substrate was irradiated with UV light of 200 mJ / cm ² using a high-pressure mercury lamp in a nitrogen atmosphere, and the pencil hardness was H A second hard coat layer was formed.

(4) Formation of optical adjustment layer (4) -1 Preparation of composition for forming high refractive index layer High refractive index coating agent (Atomics Co., Ltd., Atom Compound HUV SRZ100, nanometer as high refractive index agent 30 parts by weight of fine zirconium oxide particles), 0.9 part by weight of a photopolymerization initiator (BASF Co., Ltd., Irgacure 907), and 0.02 part by weight of a leveling agent (BYC-355, BYK-355) Parts were mixed, and 1493 parts by weight of methyl isobutyl ketone and 1493 parts by weight of cyclohexanone were diluted to prepare a composition for forming a high refractive index layer having a solid content concentration of 1% by weight.

(4) -2 Preparation of composition for forming low refractive index layer 100 parts by weight of hard coat agent (Arakawa Chemical Industries, Ltd., Beam Set 575CB), hollow silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd., Thruria 4320) 98 parts by weight of an average particle size of 50 nm), 0.9 parts by weight of a photopolymerization initiator (BASF Co., Ltd., Irgacure 907), and 0.05 parts by weight of a leveling agent (BYC-355 Co., Ltd., BYK-355) By mixing and diluting with 9700 parts by weight of methyl isobutyl ketone and 9700 parts by weight of cyclohexanone, a composition for forming a low refractive index layer having a solid content concentration of 1% by weight was prepared.
The composition of the hard coat agent (Arakawa Chemical Industries, Ltd., beam set 575CB) is as follows.
・ 95% by weight of active energy ray-curable compound containing urethane acrylate
・ Photopolymerization initiator 5% by weight

(4) -3 Formation of High Refractive Index Layer A composition for forming a high refractive index layer was applied on the first hard coat layer with a Mayer bar # 4.
Next, after drying in an oven at 70 ° C. for 1 minute, 200 mJ / cm ² of ultraviolet light was irradiated using a high-pressure mercury lamp in a nitrogen atmosphere, and the hard coat layer had a thickness of 23 nm and a refractive index of 1.87. A high refractive index layer was formed.

(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 applied by Meyer bar # 4.
Next, after drying in an oven at 70 ° C. for 1 minute, irradiation with 200 mJ / cm ² of ultraviolet rays was performed using a high-pressure mercury lamp in a nitrogen atmosphere, and a thickness of 74 nm and a refractive index of 1.39 were formed on the high refractive index layer. A low refractive index layer was formed, and an optical adjustment layer having a two-layer structure was formed on the hard coat layer.

(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 (tin oxide 10 wt%, oxidized) Sputtering on the optical adjustment layer using 90% by weight of indium to form a transparent conductive film having a square shape of 60 mm in length x 60 mm in width, 30 nm in thickness, and a surface resistance of 250 Ω / □ at the center of the optical adjustment layer did.
Next, a photoresist film patterned in a lattice shape was formed on the surface of the obtained transparent conductive film.
Next, after being etched by immersing in 10% by weight hydrochloric acid at room temperature for 1 minute, the photoresist film was removed to obtain a transparent conductive film having a patterned transparent conductive film. .
The transparent conductive film is a transparent conductive film having a thickness of 30 nm having a pattern shape in which square gaps each having a side of 2 mm are partitioned into a lattice shape on the front surface on the optical adjustment layer by a negative electrode of a transparent conductive material having a line width of 2 mm. It had a conductive film.

(6) Preparation of Protect Film Base A PET film having a thickness of 135 μm, a thermal shrinkage rate in the MD direction of 0.55%, and a thermal shrinkage rate in the TD direction of 0.04% was prepared as the protective film base material.
The thermal shrinkage rate of the protective film substrate was measured in the same manner as the thermal shrinkage rate of the transparent plastic film substrate.

(7) Formation of pressure-sensitive adhesive layer Next, an acrylic polymer having a weight average molecular weight of 600,000 and a monomer composition ratio (weight) of butyl acrylate: acrylic acid = 100: 6 (weight ratio) is formed on the surface of the prepared protective film substrate. With respect to 100 parts by weight, an adhesive composition containing 6 parts by weight of an epoxy-based crosslinking agent (“Tetrad C” manufactured by Mitsubishi Gas Chemical Co., Ltd.) is diluted with ethyl acetate to a solid content concentration of 30% by weight, Coated. Then, it dried at 90 degreeC for 1 minute, and cured at 25 degreeC for 7 days. As a result, a protective film having a pressure-sensitive adhesive layer having a gel fraction of 95% by weight and a thickness of 20 μm was obtained.

(8) Bonding of protect film Next, the second hard coat layer in the transparent conductive film and the adhesive layer in the protect film were bonded using a laminator to obtain a transparent conductive film with a protect film.
At this time, it bonded so that MD direction in a transparent plastic film base material and MD direction in a protection film base material might correspond.

2. Evaluation of Curling The degree of curling in the obtained transparent conductive film with a protective film was evaluated.
That is, the obtained transparent conductive film with a protective film was allowed to stand for 60 minutes in a furnace set at a temperature of 150 ° C. with the protective film side down.
Thereafter, the test piece was taken out of the furnace and left on the glass plate for 60 minutes in an environment of a temperature of 23 ° C. and a humidity of 50% RH with the protect film side facing down.
Then, the amount of lifting at the four corners of the test piece in the vertical direction from the glass plate surface was measured with calipers, and the maximum value among the obtained amounts of lifting was taken as the curl value. The obtained results are shown in Table 1.
In addition, since the direction of curling was reversed, the curling value was measured in the same manner because the direction of curling was reversed.

3. Visibility evaluation of patterned transparent conductive film (pattern shape visibility)
The protective film was peeled off from the transparent conductive film with a protective film used for the evaluation of curl, and the visibility of the pattern shape of the transparent conductive film was evaluated.
Specifically, the transparent conductive film is installed at a position 1 m from the white fluorescent lamp, and the white fluorescent lamp is reflected on the transparent conductive film on the same side where the white fluorescent lamp is installed. It was observed from the position of 30 cm from the transparent conductive film whether or not distortion occurred visually.
And the obtained observation result was evaluated along the following criteria. The obtained results are shown in Table 1.
In addition, as a usage mode of an actual transparent conductive film, a grid-like pattern is formed by rotating two transparent conductive films each having a transparent conductive film patterned in a line and rotating 90 °. In general, in this evaluation, for the sake of simplicity, the transparent conductive film in one transparent conductive film was formed in a lattice pattern and evaluated.
(Double-circle): About three evaluators, all evaluated that a pattern was not visually recognized under reflected light.
○: About three evaluators, two evaluated that the pattern was not visually recognized under reflected light.
X: About three evaluators, two or more evaluated that a pattern was visually recognized under reflected light.

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

[Example 3]
In Example 3, as a transparent plastic film base material, a PET film having a thickness of 60 μm, a thermal shrinkage rate in the MD direction of 0.14%, and a thermal shrinkage rate in the TD direction of 0.32% is used. A transparent conductive film with a protective film was produced in the same manner as in Example 1 except that a PET film having a thickness of 135 μm, a thermal shrinkage of 0.51% in the MD direction, and a thermal shrinkage of 0.2% in the TD direction was used. ,evaluated. The obtained results are shown in Table 1.

[Example 4]
In Example 4, 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 transparent plastic film substrate, and the thickness was used as the protective film substrate. A transparent conductive film with a protective film was produced and evaluated in the same manner as in Example 1 except that a PET film having a thermal shrinkage rate of 55 μm, MD direction heat shrinkage of 0.5% and TD direction heat shrinkage of 0.08% was used. did. The obtained results are shown in Table 1.

[Example 5]
In Example 5, a PET film having a thickness of 188 μm, a thermal shrinkage rate of 0.26% in the MD direction, and a thermal shrinkage rate of 0% in the TD direction was used as the transparent plastic film substrate, and the thickness was used as the protective film substrate. A transparent conductive film with a protective film was produced and evaluated in the same manner as in Example 1 except that a PET film having a heat shrinkage rate of 135 μm, MD direction heat shrinkage of 0.51%, and TD direction heat shrinkage of 0.2% was used. did. The obtained results are 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, an MD direction heat shrinkage ratio of 0.74%, and a TD direction heat shrinkage ratio of 0.46% is used. A transparent conductive film with a protective film was produced in the same manner as in Example 1 except that a PET film having a thickness of 135 μm, a thermal shrinkage of 0.06% in the MD direction, and a thermal shrinkage of 0.03% in the TD direction was used. ,evaluated. The obtained results are shown in Table 1.

[Comparative Example 2]
In Comparative Example 2, a PET film having a thickness of 60 μm, a thermal shrinkage rate in the MD direction of 0.74%, and a thermal shrinkage rate in the TD direction of 0.46% is used as the transparent plastic film base material. A transparent conductive film with a protective film in the same manner as in Example 1 except that a PET film having a thickness of 135 μm, a heat shrinkage ratio in the MD direction of 0.67%, and a heat shrinkage ratio in the TD direction of 0.12% was used. Were manufactured and evaluated. The obtained results are shown in Table 1.

[Comparative Example 3]
In Comparative Example 3, as a protective film substrate, a PET film having a thickness of 135 μm, a heat shrinkage rate in the MD direction of 0.67%, and a heat shrinkage rate in the TD direction of 0.12% was used. Similarly, a transparent conductive film with a protective film was produced and 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 used 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 provided on the protective film substrate side. Were manufactured and evaluated. The obtained results are shown in Table 1.

As described above in detail, according to the present invention, in the transparent conductive film with a protective film, a hard coat layer is provided on both surfaces of the transparent plastic film base, and the predetermined in the transparent plastic film base and the protective film base is provided. By setting the thermal shrinkage rate in the MD direction under the conditions to a value within a predetermined range, the occurrence of curling can be effectively suppressed even when annealing is performed.
As a result, according to the present invention, it is possible to obtain a transparent conductive film with a protective film capable of effectively suppressing the occurrence of curling, even when annealed, while being excellent in handling properties. I can do it now.
Therefore, the transparent conductive film of the present invention is expected to contribute significantly to improving the quality of display devices such as liquid crystal displays.

1: transparent conductive film, 2a: first hard coat layer, 2b: second hard coat layer, 3: transparent plastic film substrate, 4: adhesive layer, 5: protective film substrate, 6: transparent conductive film Film, 7: protective film, 8: optical adjustment layer, 8a: high refractive index layer, 8b: low refractive index layer

Claims (8)

A transparent conductive film with a protective film formed by sequentially laminating a transparent conductive film, a first hard coat layer, a transparent plastic film substrate, a second hard coat layer, and a protective film,
The protective film is composed of an adhesive layer and a protective film base material, and is laminated to be peelable from the second hard coat layer,
The first hard coat layer and the second hard coat layer, or one of them is made of a cured product of an active energy ray curable resin composition, and one molecule in the active energy ray curable resin composition A polymerizable compound (A) having two or more groups represented by the following general formula (1) and not containing an alkylene oxide unit in the remaining structure excluding the group; 15 to 85 by weight ratio (polymerizable compound (A) / polymerizable compound (B)) of 5 to 8 polymerizable compound (B) having a group represented by the following general formula (2) A value within the range of 85/15, and
The MD shrinkage in the MD direction when heated at 150 ° C. for 60 minutes in the transparent plastic film substrate is set to a value of 0.6% or less, and the MD direction when heated for 60 minutes at 150 ° C. in the protective film substrate. A transparent conductive film with a protective film, characterized in that the thermal shrinkage is 0.6% or less.

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

(In General Formula (2), R ¹ is an independent hydrogen atom or methyl group, A is an independent alkylene group having 1 to 5 carbon atoms, and the repeating number n is an independent integer of 1 or more. And * represents a binding moiety.)   The difference between the thermal shrinkage rate in the MD direction when heated at 150 ° C. for 60 minutes in the transparent plastic film substrate and the thermal shrinkage rate in the MD direction when heated at 150 ° C. for 60 minutes in the protective film substrate. The transparent conductive film with a protective film according to claim 1, wherein the transparent conductive film has a value within a range of -0.5 to 0.5%.   The heat shrinkage rate in the TD direction when heated at 150 ° C. for 60 minutes in the transparent plastic film substrate is set to a value of 0.6% or less, and the heat shrink rate in the TD direction when heated at 150 ° C. for 60 minutes in the protect film substrate. The transparent conductive film with a protective film according to claim 1 or 2, wherein the heat shrinkage is set to a value of 0.6% or less.   The transparent conductive film with a protective film is cut into a square of 100 mm in the MD direction × 100 mm in the TD direction, and the curl value when heated at 150 ° C. for 60 minutes with the protective film side down is a value of 25 mm or less. The transparent conductive film with a protective film according to claim 1, wherein the transparent conductive film has a protective film. The thickness of said 1st hard-coat layer and said 2nd hard-coat layer shall be the value within the range of 1-15 micrometers, With a protective film as described in any one of Claims 1-4 characterized by the above-mentioned. Transparent conductive film. The thickness of the said protective film base material shall be the value within the range of 10-300 micrometers, The transparent conductive film with a protective film as described in any one of Claims 1-5 characterized by the above-mentioned. The thickness of the said transparent plastic film base material shall be the value within the range of 10-200 micrometers, The transparent conductive film with a protective film as described in any one of Claims 1-6 characterized by the above-mentioned. The transparent conductive film with a protective film according to claim 1 , further comprising an optical adjustment layer between the first hard coat layer and the transparent conductive film. .

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