JP6278327B1 - Transparent conductive film, transparent conductive laminate, three-dimensional display, and resin composition - Google Patents

Abstract

Provided is a thin film, a transparent conductive film that is highly transparent and capable of exhibiting a predetermined surface protection while having stretch processability and antistatic properties. SOLUTION: The thermoplastic resin (a) is 60 to 97.9% by weight, the conductive material (b) is 1 to 30% by weight, and the fine particles (c) having an average particle diameter of 10 to 500 nm are 0.1 to 10%. A transparent conductive film for surface protection containing 1% by weight to 20% by weight and a slip agent (d), and for stretching to make the film thickness 0.2 μm or less by stretching 2.5 to 9 times The present invention relates to a transparent conductive film having a static friction coefficient and a dynamic friction coefficient of 1.5 or less and 1.0 or less, respectively, when the film thickness is 0.2 μm by a stretching process by 4 times stretching. [Selection figure] None

Description

The present invention relates to a transparent conductive film, a transparent conductive laminate, a three-dimensional display, and a resin composition.

In recent years, development of new devices characterized by shapes, such as displays with curved shapes and wearable devices with complex three-dimensional shapes, has been actively conducted, but unlike conventional devices, it can withstand molding into three-dimensional shapes and the like. There is a need for stretch processability to be obtained. In these new devices, as in the case of conventional devices, surface protection materials (hardware) with antistatic properties are added for the purpose of preventing scratches and dust adhesion during manufacturing, and ensuring a predetermined function after manufacturing. However, the conventional antistatic surface protective material does not consider the stretch processability, and a new surface protective material has to be developed.

Candidates for surface protective materials having stretch processability include, for example, curable compositions as described in Patent Documents 1 and 2, although they do not have antistatic properties. However, conventionally known surface protective materials have a trade-off relationship between stretch processability and surface protective properties (slip properties, scratch resistance, etc.), and surface protection can be achieved by increasing the crosslink density or increasing the film thickness. However, when a stretching process or the like is performed, there is a problem that the surface protection is lowered due to the occurrence of cracks or the thin film thickness. Even in Patent Document 2, it was confirmed that the predetermined surface protective properties were actually exhibited in the examples only when the film thickness was 3 μm or more, and cracks occurred at a draw ratio of 1.5 times or less. As a result, it has become difficult to meet the more advanced market demands in recent years.

When considering molding into a three-dimensional shape, the conventional surface protective material is too thick, causing excessive burden on the molding device during molding, reducing productivity, and cracking in the molded device Problems such as poor appearance and reduced surface protection tend to occur. In order to impart antistatic properties to the surface protective material, it is conceivable to add a conductive material to the surface protective material. From the viewpoint of stretch processability, a flexible conductive polymer or carbon nanomaterial is used. It is possible to use it. However, these conductive materials are highly colored components, and when applied to conventional thick-film surface protective materials, there is a problem in use in applications that require transparency, including displays, due to the strong color tendency. Therefore, also in this respect, there is a problem in applying the conventional surface protective material to the above-described new device.

JP-A-2015-193747 JP-A-8-108695

There has been a demand for the development of a thin film, a material that is highly transparent and capable of exhibiting a predetermined surface protection property while having stretch processability and antistatic properties.

As a result of intensive studies, the present inventors have determined that the static friction coefficient and the dynamic friction coefficient after the stretching process have specific numerical values even when the thin film has a thickness of 0.2 μm or less by stretching process by 2.5 to 9 times stretching. It is found that surface protection that can withstand practical use can be exhibited by suppressing to the following, and further, in a specific formulation, the thermoplastic resin (a) is a conductive material (b), and the average particle size is 10 to 500 nm. It was found that a transparent conductive film for surface protection satisfying various requirements can be obtained by combining the fine particles (c) and the slip agent (d), and the present invention has been completed.

That is, the present invention relates to:
[1] 60-97.9 wt% of thermoplastic resin (a), 1-30 wt% of conductive material (b), 0.1-10 wt% of fine particles (c) having an average particle size of 10-500 nm %, And a transparent conductive film for surface protection containing 1 to 20% by weight of the slip agent (d), and is subjected to a stretching process in which the film thickness is 0.2 μm or less by stretching 2.5 to 9 times. A transparent conductive film having a static friction coefficient and a dynamic friction coefficient of 1.5 or less and 1.0 or less, respectively, when the film thickness is 0.2 μm by stretching by 4 times stretching;
[2] The transparent conductive film according to [1], wherein the thermoplastic resin (a) is at least one selected from the group consisting of an ester resin, a urethane resin, an acrylic resin, and a polyether resin;
[3] The transparent conductive film according to [1] or [2], wherein the conductive material (b) is a conductive polymer and / or a carbon nanomaterial;
[4] The transparent conductive film according to [1] to [3], wherein the fine particles (c) are inorganic fine particles and / or organic fine particles having a crosslinked structure;
[5] The transparent conductive film according to [1] to [4], wherein the slip agent (d) is a silicone resin and / or a fluorine resin;
[6] A transparent conductive laminate in which the transparent conductive film of [1] to [5] is disposed on a substrate;
[7] The transparent conductive laminate according to [6], wherein the substrate is a thermoplastic resin substrate;
[8] The transparent conductive laminate according to [6] or [7], wherein an acrylic pressure-sensitive adhesive layer and / or a urethane-based easy adhesion layer is further disposed;
[9] The transparent conductive laminate according to [6] to [8], which is disposed in the order of the transparent conductive film, the substrate, the acrylic adhesive layer, and / or the urethane-based easy adhesion layer according to [1] to [5];
[10] A three-dimensional display including the transparent conductive laminate according to [6] to [9];
[11] 60-97.9 wt% of thermoplastic resin (a), 1-30 wt% of conductive material (b), 0.1-10 wt% of fine particles (c) having an average particle size of 10-500 nm %, And a resin composition for forming a transparent conductive film according to [1] to [5], comprising 1 to 20% by weight of a slip agent (d); and
[12] The resin composition according to [11], comprising water or a water-alcohol mixed solvent as the solvent (f), having a solid content of 10% or less and a pH of 4 to 10.

Even when the transparent conductive film of the present invention is a thin film having a thickness of 0.2 μm or less by stretching by stretching by 2.5 to 9 times, a conductive material (b ), By using a combination of the fine particles (c) having an average particle diameter of 10 to 500 nm and the slip agent (d), the static friction coefficient measured using a resin film having a specific surface roughness after stretching and As a result of suppressing the dynamic friction coefficient to a specific value or less, the required surface protection and antistatic properties can be exhibited even when it is applied to a device that needs to be stretched or molded into a three-dimensional shape. .

<< Transparent conductive film >>
First, the transparent conductive film of the present invention will be described.
The transparent conductive film of the present invention contains 0 to 97.9 wt% of the thermoplastic resin (a), 1 to 30 wt% of the conductive material (b), and 0 fine particles (c) having an average particle diameter of 10 to 500 nm. A transparent conductive film for surface protection containing 1 to 10% by weight and 1 to 20% by weight of the slip agent (d), and the film thickness is 0.2 μm or less by stretching 2.5 to 9 times The static friction coefficient and the dynamic friction coefficient are 1.5 or less and 1.0 or less, respectively, when the film thickness is 0.2 μm by the stretching process by 4 times stretching. And

<Thermoplastic resin (a)>
The thermoplastic resin (a) is not particularly limited, and examples thereof include ester resins, urethane resins, acrylic resins, olefin resins, carboxyl group-containing resins, and polyether resins. These may be used alone or in combination of two or more. Among these, ester resins, urethane resins, acrylic resins and polyether resins are preferably used for the following reasons, and in particular, those obtained by combining one or more types of polyether resins with other thermoplastic resins are preferably used. . The thermoplastic resin (a) is preferably an aqueous thermoplastic resin that can be dissolved or dispersed in water in order to facilitate blending with the conductive material (b) described later, and the thermoplastic resin has a hydrophilic functional group. May be solubilized or dispersed as a result of being applied, or may be forcibly solubilized or dispersed by an emulsifier.

As will be described later, in the transparent conductive film, it is necessary to keep the content of the conductive material (b) and the slip agent (d) low, but when the thermoplastic resin (a) is used as a main solid component, it is thermosetting. Compared to the case where resin or photo-curable resin is used as the main solid component, the network structure during film formation is fluid, so that the conductive material (b) and slip agent (d) are on the film surface or in the vicinity thereof. There is a tendency to localize. Therefore, even if these components contained in the entire transparent conductive film are relatively small, the antistatic property and slip property can be maintained at a level that requires the conductive material (b) and the slip agent (d) localized on or near the film surface. Therefore, it is particularly important to use the above-described thermoplastic resin (a) in the transparent conductive film of the present invention. Moreover, it is important to use the thermoplastic resin (a) in the transparent conductive film of the present invention in order to ensure stretch processability.

The ester resin is not particularly limited as long as it is a polymer compound obtained by polycondensation of a compound having two or more carboxyl groups in the molecule and a compound having two or more hydroxyl groups. Examples include terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. These may be used alone or in combination of two or more.

The urethane resin is not particularly limited as long as it is a polymer compound obtained by copolymerizing a compound having an isocyanate group and a compound having a hydroxyl group. For example, an ester / ether polyurethane, an ether polyurethane, or a polyester Examples thereof include polyurethane, carbonate polyurethane, and acrylic polyurethane. These may be used alone or in combination of two or more.

The acrylic resin may be polymerized with a copolymerizable monomer as long as it contains a (meth) acrylic monomer as a main constituent monomer. When polymerized with a copolymerizable monomer, (meth) acrylic At least one should just have an acid group among a system monomer and a copolymerizable monomer. Examples of the acrylic resin include (meth) acrylic monomers having an acid group [(meth) acrylic acid, sulfoalkyl (meth) acrylate, sulfonic acid group-containing (meth) acrylamide, etc.] or copolymers thereof, acids (Meth) acrylic monomer which may have a group, and other polymerizable monomer having an acid group [other polymerizable carboxylic acid, polymerizable polycarboxylic acid or anhydride, vinyl aromatic sulfonic acid Etc.] and / or a copolymer with the above copolymerizable monomer [eg, (meth) acrylic acid alkyl ester, glycidyl (meth) acrylate, (meth) acrylonitrile, aromatic vinyl monomer, etc.], acid group (Meth) acrylic copolymerizable monomer [for example, (meth) acrylic acid alkyl ester, hydroxyalkyl (meth) acrylate, glycidyl ( Data) acrylate, copolymers of (meth) acrylonitrile, etc.], rosin-modified urethane acrylate, special modified acrylic resins, urethane acrylates, epoxy acrylates, and urethane acrylates emulsion and the like. Among these, (meth) acrylic acid- (meth) acrylic acid ester polymers (acrylic acid-methyl methacrylate copolymer, etc.), (meth) acrylic acid- (meth) acrylic acid ester-styrene copolymers ( Acrylic acid-methyl methacrylate-styrene copolymer, etc.) are preferred.

The olefin resin is not particularly limited, and examples thereof include chlorinated polypropylene, non-chlorinated polypropylene, chlorinated polyethylene, and non-chlorinated polyethylene. These may be used alone or in combination of two or more.

The polyether resin is not particularly limited, and examples thereof include polyalkylene glycol, polyvinyl alcohol, polyether polyol, polyglycerin, pullulan, and derivatives thereof. These may be used alone or in combination of two or more.

The carboxyl group-containing resin is not particularly limited. For example, a ring-opening, half-esterification, or half-amidation of an acid anhydride of a copolymer of a vinyl monomer such as styrene, ethylene, methyl vinyl ether and maleic anhydride. Resin and the like. These may be used alone or in combination of two or more.

In the transparent conductive film of the present invention, the content of the thermoplastic resin (a) may be 60 to 97.9% by weight, preferably 65 to 95% by weight, more preferably 70 to 90% by weight. is there. When the content of the thermoplastic resin (a) is within the above range, it is possible to keep the content of the conductive material (b) and the slip agent (d) low while exhibiting good stretch processability. In addition, in this invention, extending | stretching workability means the easiness of shaping | molding in the case of pressure molding, and the extending | stretching followability in the extending | stretching process.

<Conductive material (b)>
Although it does not specifically limit as a conductive material (b), For example, a conductive polymer, a carbon nanomaterial, etc. are mentioned. From the viewpoint of obtaining good stretch processability in the transparent conductive film of the present invention, a conductive polymer and / or a carbon nanomaterial is preferable. These may be used alone or in combination of two or more.

The conductive polymer is not particularly limited, and a conventionally known conductive polymer can be used. Specific examples thereof include polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene vinylene, polynaphthalene, and derivatives thereof. Can be mentioned. These may be used alone or in combination of two or more. Among these, a conductive polymer including at least one thiophene ring in the molecule is preferable in that a molecule having high conductivity can be easily formed by including a thiophene ring in the molecule. The conductive polymer may form a complex with a dopant such as polyanion.

Among conductive polymers containing at least one thiophene ring in the molecule, poly (3,4-disubstituted thiophene) is more preferable because it is extremely excellent in conductivity and chemical stability. Further, when the conductive polymer is poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and polyanion (dopant), the temperature is low and the time is short. Thus, a conductive composite material can be formed, and productivity is also excellent. The polyanion is a conductive polymer dopant, and the content thereof will be described later.

［式中、Ｒ^１及びＲ^２は相互に独立して水素原子又はＣ_１−４のアルキル基を表すか、又は、Ｒ^１及びＲ^２が結合している場合にはＣ_１−４のアルキレン基を表す］。 Poly (3,4-disubstituted thiophene) is particularly preferably poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene). As poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene), a cationic polythiophene composed of repeating structural units represented by the following formula (1) is preferable:

[Wherein, R ¹ and R ² independently represent a hydrogen atom or a C _1-4 alkyl group, or, when R ¹ and R ² are bonded, C _1-4 alkylene, Represents a group].

The C _1-4 alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. . In addition, when R ¹ and R ² are bonded, the C _1-4 alkylene group is not particularly limited, and examples thereof include a methylene group, a 1,2-ethylene group, a 1,3-propylene group, 1, 4-butylene group, 1-methyl-1,2-ethylene group, 1-ethyl-1,2-ethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, etc. Can be mentioned. Among these, a methylene group, 1,2-ethylene group, and 1,3-propylene group are preferable, and a 1,2-ethylene group is more preferable. In the C _1-4 alkyl group and the C _1-4 alkylene group, a part of hydrogen may be substituted. As the polythiophene having a C _1-4 alkylene group, poly (3,4-ethylenedioxythiophene) is particularly preferable.

Although it does not specifically limit as a dopant, A poly anion is mentioned. The polyanion forms a complex by forming an ion pair with the polythiophene (derivative), and the polythiophene (derivative) can be stably dispersed in water. Although it does not specifically limit as a poly anion, For example, carboxylic acid polymers (for example, polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.), sulfonic acid polymers (for example, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyisoprene) Sulfonic acid etc.). These carboxylic acid polymers and sulfonic acid polymers are also copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers such as aromatic vinyl compounds such as acrylates, styrene, vinyl naphthalene, etc. It may be. Among these, polystyrene sulfonic acid is particularly preferable.

The complex of the conductive polymer and the polyanion is preferably a complex of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid because it is particularly excellent in conductivity.

Examples of the carbon nanomaterial include a carbon nanotube, a carbon nanohorn, a carbon nanowall, and fullerene. Among these, it is preferable to use carbon nanotubes from the viewpoint that good antistatic properties can be exhibited when a transparent conductive film is formed. Carbon nanotubes generally have a hollow fiber shape, and are carbon materials having a diameter of 0.5 nm to 5 μm and a length of about 10 nm to 1000 μm. Carbon nanotubes having a diameter of 0.5 nm to 1 μm and a length of 10 nm to 100 μm are used. It can be preferably used.

In the transparent conductive film of the present invention, the content of the conductive material (b) may be 1 to 30% by weight, preferably 2 to 25% by weight, and more preferably 4 to 20% by weight. When the content of the conductive material (b) is within the above range, sufficient transparency can be achieved while exhibiting good antistatic properties.

In addition, since the transparent conductive film of the present invention uses the thermoplastic resin (a) as a main solid component, the conductive material (b) is localized at or near the film surface at the time of film formation, and thus exhibits antistatic properties. In comparison with the content per unit area of the conductive material (b), which is normally required, a predetermined antistatic property can be exhibited even with a small content, so that the transparency expressed by the total light transmittance and the haze value is further improved. There are advantages that can be achieved well.

<Fine particles (c) having an average particle size of 10 to 500 nm>
The fine particles (c) having an average particle size of 10 to 500 nm are not particularly limited as long as the average particle size is 10 to 500 nm, but the average particle size of the fine particles (c) is preferably 20 to 200 nm. . When the average particle size is in the above range, the static friction coefficient is lowered by appropriately increasing the surface roughness of the transparent conductive film. As a result, the haze value before and after the stretching process is kept low while suppressing the occurrence of scratches. , Think that good transparency can be achieved. Further, the fine particles (c) having an average particle diameter of 10 to 500 nm are preferably those that can be dispersed in water in order to facilitate blending with the conductive material (b), and impart hydrophilic functional groups to the fine particles. As a result, it may be dispersed, or it may be forcibly dispersed by a dispersant.

The average particle diameter in the present specification is a value measured by measuring the diameter of 50 to 100 arbitrary particles with a scanning electron microscope (SEM) and adopting the average particle diameter based on the number. Say.

Examples of the fine particles (c) having an average particle diameter of 10 to 500 nm include inorganic fine particles and / or organic fine particles having a crosslinked structure.

Examples of the inorganic fine particles include, but are not limited to, silica fine particles such as colloidal silica, hollow silica and fumed silica, metal oxide fine particles such as titania and zirconia, thermoplastic or thermosetting acrylic resins. Core-shell type acrylic-silica composite particles coated with silica, core-shell type melamine-silica composite particles coated with melamine resin with silica, and core-shell type acrylic-silica coated with a thermoplastic or thermosetting acrylic resin Organic-inorganic composite particles such as composite particles, core-shell type melamine-silica composite particles in which silica particles are coated with melamine resin, and acrylic-silica composite particles in which small silica particles are supported by thermoplastic or thermosetting acrylic particles Can be mentioned. These may be used alone or in combination of two or more.

The organic fine particles having a crosslinked structure are not particularly limited, and examples thereof include fluororesin fine particles, acrylic resin fine particles, melamine resin fine particles, and urethane rubber fine particles. These may be used alone or in combination of two or more.

The content of the fine particles (c) is preferably 0.1 to 10% by weight, more preferably 1.5 to 10% by weight, and still more preferably 2 to 10% by weight. When content of microparticles | fine-particles (c) is in the said range, a static friction coefficient can be reduced and scratch resistance can be improved, maintaining transparency after extending | stretching process in a transparent conductive film.

<Slip agent (d)>
The slip agent (d) is not particularly limited, and examples thereof include hydrocarbon resins, oxy fatty acids, aliphatic alcohols, silicone resins, and fluorine resins. These may be used alone or in combination of two or more. Furthermore, the slip agent (d) is preferably one that can be dissolved or dispersed in water or alcohol in order to facilitate blending with the conductive material (b), and the result of imparting a hydrophilic functional group to the slip agent. Those solubilized or dispersed are particularly preferred.

Examples of the hydrocarbon resin include low molecular weight wax, paraffin wax, polyethylene wax, and chlorinated hydrocarbon. Examples of the oxy fatty acid include higher fatty acids such as lauric acid, stearic acid, and behenic acid, and hydroxy stearic acid. Examples of the aliphatic alcohol include stearyl alcohol, lauryl alcohol, and palmityl alcohol. Silicone resins include polyethers and / or polysiloxanes having hydrophilic group-containing alkyl groups in the side chain, block polymers of polyether and polysiloxane, block polymers of acrylic resin and polysiloxane, and polysiloxanes in the side chain. Examples thereof include acrylic resins having polyether and polysiloxane in the side chain.

Fluorocarbon resins include tetrafluoroethylene, perfluoroalkyl sulfonic acid amide, perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trimethyl ammonium salt, perfluoroalkyl amino. Examples thereof include sulfonates, perfluoroalkyl phosphate esters, perfluoroalkylalkyl compounds, perfluoroalkylalkyl betaines, perfluoroalkyl halides, and fluorine-containing / hydrophilic group-containing oligomers containing them.

From the standpoint of achieving both slip and transparency, silicone resins and / or fluorine resins are preferred.

In the transparent conductive film of the present invention, the content of the slip agent (d) may be 1 to 20% by weight, preferably 2.5 to 20% by weight, and more preferably 4 to 20% by weight. When the content of the slip agent (d) is within the above range, the dynamic friction coefficient can be sufficiently lowered to suppress the growth of scratches, and the haze value increase after the stretching process can be suppressed to a low level.

The transparent conductive film of the present invention may further contain a curable resin (e) as long as the stretch processability is not impaired for the purpose of obtaining higher scratch resistance. Although it does not specifically limit as curable resin (e), For example, the compound, isocyanate resin, melamine resin, and silicate resin containing an epoxy group are mentioned. These may be used alone or in combination of two or more. A melamine resin is preferable from the viewpoint of maintaining good stretch processability while enhancing scratch resistance. Further, the curable resin (e) is preferably dispersible in water or alcohol in order to facilitate blending with the conductive material (b), and is dispersed as a result of imparting hydrophilic functional groups to the fine particles. It may be one that has been dispersed or may be forcibly dispersed by a dispersant.

［式中、Ｘは、−ＮＲ^１Ｒ^１’であり；
Ｙは、−ＮＲ^２Ｒ^２’であり；
Ｚは、−ＮＲ^３Ｒ^３’であり；
Ｒ^１、Ｒ^１’、Ｒ^２、Ｒ^２’、Ｒ^３及びＲ^３’は、それぞれ独立して、水素原子、Ｃ_１−５のアルキル基又はＣ_１−５のヒドロキシアルキル基であり、ここで、Ｃ_１−５のアルキル基及びＣ_１−５のヒドロキシアルキル基は、それぞれ独立して、１個以上の酸素原子で中断されていてもよい］。 Although it does not specifically limit as a melamine resin, For example, the melamine resin which consists of a monomer represented by the following General formula (2) is mentioned.

[Wherein X is —NR ¹ R ^{1 ′} ;
Y is —NR ² R ^{2 ′} ;
Z is —NR ³ R ^{3 ′} ;
R ¹ , R ^{1 ′} , R ² , R ^{2 ′} , R ³ and R ^{3 ′} are each independently a hydrogen atom, a C _1-5 alkyl group or a C _1-5 hydroxyalkyl group, And the C _1-5 alkyl group and the C _1-5 hydroxyalkyl group may each independently be interrupted by one or more oxygen atoms.

When the transparent conductive film of this invention contains curable resin (e), it is preferable that it is 0.1 to 5 weight%, and it is more preferable that it is 0.1 to 3 weight%. When the compounding quantity of curable resin (e) exists in the said range, scratch resistance can be improved, maintaining the stretch workability in the transparent conductive film of this invention.

The transparent conductive film of this invention may contain components, such as a ultraviolet absorber and antioxidant, further as needed.

The stretching process is not particularly limited as long as it involves 2.5 to 9 times stretching, but the stretching ratio is preferably 3 to 7 times, for example, and 4 to 6 times. Is more preferable. When the stretching is within the above range, it is possible to process into a desired shape and develop high transparency while suppressing the decrease in conductivity and scratch resistance due to stretching.

Although it will not specifically limit if the film thickness after an extending | stretching process is 0.2 micrometer or less, For example, it is preferable that it is 0.15 micrometer or less, and it is more preferable that it is 0.1 micrometer or less. When the film thickness is 0.2 μm or less, it is possible to prevent a decrease in transparency due to the conductive material (b) and the like.

In the transparent conductive film of the present invention, in order to obtain good scratch resistance, it is particularly important to adjust the static friction coefficient and the dynamic friction coefficient after stretching so as to be within a predetermined numerical range. When the film thickness is 0.2 μm, the static friction coefficient when rubbing with a resin film having a surface roughness (Ra) of 0.1 μm or less needs to be 1.5 or less, and is 0.8 or less. It is preferable that the ratio is 0.4 or less. Similarly, when the film thickness is 0.2 μm, the dynamic friction coefficient needs to be 1.0 or less, preferably 0.6 or less, and more preferably 0.3 or less. When the static friction coefficient is 1.5 or less, the scratch starting point is less likely to occur, and when the dynamic friction coefficient is 1.0 or less, it is possible to suppress the growth of the scratch and suppress the appearance of the scratch. In addition, scratch resistance that can withstand practical use is exhibited even with a flexible substrate.

The static friction coefficient and the dynamic friction coefficient in this specification refer to those measured by the measurement method described in the following examples.

In addition, since the transparent conductive film of the present invention is subjected to stretching, it is necessary to have a certain stretching resistance. For example, when the film is formed to a film thickness of 0.4 μm and subjected to a stretching process 4 times. The haze value is preferably 3 times or less that before the stretching treatment. When the transparent conductive film having a film thickness of 0.4 μm is subjected to a stretching process of 4 times and the haze value is 3 times or less before the stretching process, the transparent conductive film after being subjected to the stretching process is still good. In order to maintain high transparency, it can be used in applications where transparency is required. In the present specification, “stretching 4 times” means that the base material is stretched until the length in the longitudinal direction is doubled and the length in the lateral direction is doubled.

The haze value in this specification refers to what is measured by the measuring method described in the following examples.

Furthermore, similarly to the haze value, for example, when the film is formed to a film thickness of 0.4 μm and then subjected to a 4-fold stretching process, the surface resistivity is preferably 1000 times or less before the stretching process. When the transparent conductive film having a thickness of 0.4 μm is subjected to a stretching process of 4 times and the surface resistivity is 1000 times or less before the stretching process, the transparent conductive film after being subjected to the stretching process is still In order to maintain good antistatic properties, it can be used in applications where antistatic properties are required.

<< Transparent conductive laminate >>
The transparent conductive laminate of the present invention is characterized in that the transparent conductive film of the present invention is disposed on a substrate.

Although it does not specifically limit as a base material, From the point which can be used by an extending | stretching process, it is preferable that it is a thermoplastic resin base material. The thermoplastic resin base material is not particularly limited. For example, amorphous polyethylene terephthalate (A-PET), polyester resin such as modified polyester, polyethylene (PE) resin, polypropylene (PP) resin, polystyrene resin , Polyolefin resins such as cyclic olefin resins, vinyl resins such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin, polysulfone (PSF) resin, polyether sulfone (PES) resin, polycarbonate ( PC) resin, polyamide resin, polyimide resin, acrylic resin, triacetyl cellulose (TAC) resin and the like are used. Amorphous polyethylene terephthalate (A-PET), polyolefin resins and acrylic resins, and triacetyl cellulose (TAC) resins are preferred from the viewpoints of flexibility, transparency, easy moldability, and the like. These thermoplastic resins may be used alone or in combination of two or more. Among these, a thermoplastic resin base material using an amorphous resin and having an in-plane and thickness direction retardation value of 20 nm or less is particularly preferable.

Although the thickness of a base material is not specifically limited, It is preferable that it is 40-900 micrometers, It is more preferable that it is 80-800 micrometers, It is further more preferable that it is 120-600 micrometers. This is because, when the thickness of the substrate is within the above range, it is possible to secure a high degree of transparency and mechanical strength that can withstand various processing processes when the film is stretched 4 to 8 times while sufficiently maintaining the stretch processability. .

In the transparent conductive laminate of the present invention, in order to enable attachment to a liquid crystal cell, OLED cell, touch sensor, etc., and to facilitate device assembly, an acrylic pressure-sensitive adhesive layer and / or a urethane-based easy adhesion layer, An ultraviolet curable adhesive layer is preferably disposed.

Since the transparent conductive film of the present invention is made thinner than a normal surface protective material for the purpose of being subjected to stretching processing, depending on the processing process, there may be a problem in terms of dimensional stability, but good dimensional stability. It is preferable to further dispose an acrylic pressure-sensitive adhesive layer and / or a urethane-based easy-adhesion layer from the viewpoint of the property. From the viewpoint of ensuring better dimensional stability, the acrylic adhesive layer and / or the urethane-based easy adhesion layer is disposed on a surface different from the surface on which the transparent conductive film of the present invention is disposed on the substrate. It is preferable.

As the acrylic resin that can be used in the acrylic adhesive layer, those that are soluble in an organic solvent are preferred. For example, butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, (meth) A (meth) acrylic acid ester base polymer such as 2-ethylhexyl acrylate and a copolymer base polymer using two or more of these (meth) acrylic acid esters are preferably used. Further, polar monomers may be copolymerized with these base polymers. As polar monomers, (meth) acrylic acid, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) Examples thereof include monomers having a carboxy group, a hydroxyl group, an amide group, an amino group, an epoxy group, and the like such as acrylate.

These acrylic resins can be used alone, but may contain a crosslinking agent. As the crosslinking agent, a divalent or polyvalent metal ion that forms a carboxylic acid metal salt with a carboxyl group, a polyamine compound that forms an amide bond with a carboxyl group, Examples thereof include polyepoxy compounds and polyols that form an ester bond with a carboxyl group, and polyisocyanate compounds that form an amide bond with a carboxyl group. Among these, a polyisocyanate compound is widely used as an organic crosslinking agent, has excellent transparency, weather resistance, heat resistance, retains appropriate wettability and cohesion, and exhibits appropriate pressure-sensitive adhesive properties. This is because the layer design is facilitated.

The urethane resin that can be used in the urethane-based easy-adhesion layer can be obtained, for example, by reacting a polyol, a polyisocyanate, and a chain extender having a free carboxyl group. The polyol is not particularly limited as long as it has two or more hydroxyl groups in the molecule, and any appropriate polyol can be used. For example, polyacryl polyol, polyester polyol, polyether polyol and the like can be mentioned. These can be used alone or in combination of two or more.

The polyisocyanate is not particularly limited as long as it has two or more isocyanate groups in the molecule, and any appropriate polyisocyanate can be used. For example, aliphatic isocyanate, aromatic isocyanate, etc. are mentioned. These can be used alone or in combination of two or more.

Examples of the chain extender having a free carboxyl group include dihydroxycarboxylic acid and dihydroxysuccinic acid. Examples of the dihydroxycarboxylic acid include dialkylolalkanoic acids such as dimethylolalkanoic acid (for example, dimethylolacetic acid, dimethylolbutanoic acid, dimethylolpropionic acid, dimethylolbutyric acid, dimethylolpentanoic acid). These can be used alone or in combination of two or more.

These urethane resins can be used alone, but may contain a crosslinking agent. As a crosslinking agent, the crosslinking agent which has an epoxy group is mentioned. The epoxy crosslinking agent is not particularly limited as long as it has at least one epoxy group in the molecule. Examples thereof include bisphenol type epoxy compounds, novolak type epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, glycidylamine type epoxy compounds, halogenated epoxy compounds and the like.

These urethane resins and cross-linking agents include water-based ones and organic solvent-based ones, but water-based ones are preferable in consideration of stretch processability.

The UV curable adhesive layer includes a compound having an epoxy group or an oxetane group mixed with a photocationic polymerization initiator, a compound having a (meth) acrylic group mixed with a photo radical polymerization initiator, Those used in combination are preferably used.

Examples of the compound having an epoxy group or oxetane group include polyfunctional alicyclic epoxy resins, polyfunctional glycidyl ether resins, and polyfunctional oxetane resins based on monofunctional alicyclic for the purpose of lowering viscosity. An epoxy resin, a monofunctional fat glycidyl ether resin, or a monofunctional fat oxetane resin may be used in combination.

As the photocationic polymerization initiator, a phosphate compound, an antimonate compound, or an iodonium compound is preferably used. Generally, the photocationic polymerization initiator is 0 with respect to 100 parts by weight of the compound having an epoxy group or an oxetane group. .1-10 parts by weight are mixed. Moreover, in order to improve the performance of the cationic photopolymerization initiator, a thioxanthone photosensitizer or a benzophenone photosensitizer may be further used in combination.

Examples of the compound having a (meth) acryl group include, in addition to ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like, polyfunctional urethane acrylate and polyfunctional epoxy. Acrylate is also preferably used.

Examples of the radical photopolymerization initiator include benzophenone-based, thioxanthone-based, acetophenone-based, and acylphosphine-based, and generally 0.1 to 10 parts by weight with respect to 100 parts by weight of the compound having a (meth) acryl group. Mixed.

The transparent conductive laminate having such an ultraviolet curable adhesive layer is bonded to another functional film or device and the ultraviolet curable adhesive layer surface after stretching, and is subjected to i-line (365 nm), h-line (405 nm), and g-line. By irradiating ultraviolet rays including (436 nm) or the like with an illuminance of 10 to 1200 mW / cm ² and an irradiation light amount of 20 to 2500 mJ / cm ² , it can be easily bonded to other functional films and devices.

In addition, in the transparent conductive laminate of the present invention, in addition to the transparent conductive film of the present invention, the substrate, the acrylic adhesive layer, the urethane-based adhesive layer, and the ultraviolet curable adhesive layer, the polarizing layer, the retardation layer, and the viewing angle compensation Layers and the like can also be arranged.

When the acrylic pressure-sensitive adhesive layer is disposed in the transparent conductive laminate of the present invention, the thickness of the acrylic pressure-sensitive adhesive layer is not particularly limited, and is preferably 20 to 100 μm after stretching, for example, more preferably 40. ˜80 μm.
When a urethane type easily bonding layer is arrange | positioned, the thickness of a urethane type easily bonding layer is not specifically limited, For example, it is preferable that it is 0.04-20 micrometers after an extending | stretching process, More preferably, it is 0.05-5 micrometers. It is.
When the ultraviolet curable adhesive layer is disposed, the thickness of the ultraviolet curable adhesive layer is not particularly limited, and is preferably, for example, 0.1 to 20 μm, more preferably 0.5 to 5 μm after stretching. It is.
When the thickness of the acrylic adhesive layer, urethane easy-adhesive layer, and UV-curable adhesive layer is within the above range, the transparent conductive layer does not interfere with the prescribed performance of the transparent conductive laminate, such as good stretchability and transparency. The dimensional stability of the laminate can be ensured.

Since the transparent conductive laminate of the present invention is excellent in stretch followability, it can be subjected to stretching. The method for stretching the transparent conductive laminate is not particularly limited, and examples thereof include roll stretching, heat molding, vacuum molding, press molding, pressure molding, and blow molding.

Although it does not specifically limit as conditions at the time of extending | stretching the transparent conductive laminated body of this invention, It is preferable to shape | mold at 20-200 degreeC for 0.1 to 30 minutes.

<< Resin composition >>
The resin composition of the present invention is for forming the transparent conductive film of the present invention. When the transparent conductive film of the present invention is formed by coating, a solvent (f) may be further included for the purpose of obtaining good coatability.

Although it does not specifically limit as a solvent (f), For example, alcohol, such as water, methanol, ethanol, 2-propanol, 1-propanol, glycerol; Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol Ethylene glycols such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, etc .; glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate Class: propylene glycol, dipropylene glycol Propylene glycols such as tripropylene glycol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene Propylene glycol ethers such as glycol diethyl ether; propylene glycol ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate; L-furan; acetone; acetonitrile; isophorone; propylene carbonate; γ-butyrolactone; β-butyrolactone; 2-phenoxyethanol; dioxane; morpholine; 4-acryloylmorpholine; 1,3-dimethyl-2-imidazolidinone; N, N-dimethylacetamide; N-methylformamide; N, N-dimethylformamide; acetamide; N-ethylacetamide; N-phenyl-N-propylacetamide; Sulfoxide; β-thiodiglycol; triethylene glycol; tripropylene glycol; 1,4-butanediol; 1,5-pentanediol; 1,3-butanediol; Ol; neopentyl glycol; catechol; cyclohexane diol; cyclohexane dimethanol; glycerin; erythritol; immitol; lactitol; maltitol; mannitol; Ε-caprolactam; laurolactam and the like. These may be used alone or in combination of two or more. From the viewpoint of the coating property and storage stability of the resin composition, water and a mixed solvent containing water are preferable.

Although it does not specifically limit as a solvent used by mixing with water, The work safety at the time of extending | stretching at the high temperature of 100 degreeC or more simultaneously with application | coating improves the electroconductivity of a conductive polymer. From the viewpoint of safety, the boiling point of glycerin, ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol, N, N-dimethylacetamide, N-methylformamide, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, etc. A solvent of 100 ° C. or higher is preferable. These may be used alone or in combination of two or more.

When the resin composition of the present invention contains the solvent (f), the content of the solvent (f) is preferably a blending amount that makes the solid content of the resin composition of the present invention 10% or less, and is particularly limited. However, the solid content of the resin composition of the present invention is more preferably 7% or less, and further preferably 5% or less. When the solid content of the resin composition of the present invention is 10% or less, the coating property is good when the thin film is formed, and the storage stability is also excellent.

Moreover, when the resin composition of this invention contains a solvent (f), it is preferable that the pH of the resin composition of this invention is 4-10, It is more preferable that it is 5-9, It is 6-9 More preferably. When the pH of the resin composition of this invention exists in the said range, it is excellent in storage stability and corrosion of a coating equipment can be reduced.

The resin composition of the present invention may further contain components such as an ultraviolet absorber, an antioxidant, an antiseptic, a release agent, an antifoaming agent, a leveling agent, and a polymerization initiator as necessary.

<< Method for producing transparent conductive film and transparent conductive laminate >>
Although the transparent conductive film of this invention can be manufactured by making the resin composition of this invention into a coating film, for example, a well-known method can be used as a method of forming a coating film, It does not specifically limit. However, for example, roll coating, bar coating, dip coating, spin coating, casting, die coating, blade coating, gravure coating, curtain coating, spray coating, doctor coating, slit coating, etc. The method of forming a coating film on a base material by is mentioned.

The method of drying the resin composition of the present invention applied on the substrate is not particularly limited, but it is 0 at 20 to 200 ° C. using a blast drying facility, a vacuum drying facility, an IR drying facility, a hot plate, or the like. And a method of drying for 1 to 30 minutes. If necessary, corona treatment or UV excimer treatment can be performed on the substrate in advance to improve wettability.

When the transparent conductive film of the present invention is formed on a substrate and used as it is as the transparent conductive laminate of the present invention, it can be stretched simultaneously with film formation. Furthermore, if necessary, an acrylic pressure-sensitive adhesive layer, a urethane-based easy-adhesion layer, and other functional layers can be simultaneously formed when the transparent conductive film is formed on the substrate and stretched at the same time.

<< 3D display >>
The three-dimensional display according to the present invention includes the transparent conductive laminate according to the present invention. Since the transparent conductive laminate of the present invention is excellent in stretch processability, it can be formed into an arbitrary three-dimensional shape and is excellent.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
In the following examples, “part” or “%” means “part by weight” or “% by weight”, respectively, unless otherwise specified.

1-1. Conductive material / PEDOT: PSS aqueous dispersion (prepared in Production Example 1, solid content: 1.3% by weight)
-Carbon nanotube aqueous dispersion (prepared in Production Example 2, solid content ratio 1.1% by weight)
1-2. Thermoplastic resin / acrylic resin (manufactured by Toagosei Co., Ltd., Jurimer FC-80, solid content 30%, glass transition temperature 50 ° C.)
-Polyurethane (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 830HS, solid content 35%, glass transition temperature 68 ° C)
Polyester (Toagosei Co., Ltd., Aronmelt PES-2405A30, solid content rate 30%, glass transition temperature 40 ° C.)
・ Polyether (Daiichi Kogyo Seiyaku Co., Ltd., Evan U-103, solid content: 100%)
1-3. Thermosetting resin / melamine (DIC Corporation, Becamine M-3, solid content rate 77%)
1-4. Photo-curing resin / urethane acrylate (Daicel Ornex Co., Ltd., UCECOAT7655, solid content 35%)
1-5. Slip agent / polyether-modified silicone (Toray Dow Corning Co., Ltd., 57 ADDITIVE, 100% solid content)
Fluorine group-containing oligomer (manufactured by DIC Corporation, MegaFuck F-477, solid content rate 100%)
1-6. Fine particles / silica fine particles (manufactured by CIK Nanotech Co., Ltd., SIRW15WT% -H27, solid content 15%, average particle diameter 20 nm)
Silica fine particles (Nippon Shokubai Co., Ltd., Seahoster KE-W50, solid content 20%, average particle size 500 nm)
・ Acrylic resin fine particles (Nippon Shokubai Co., Ltd., Epostor MX050W, solid content 10%, average particle size 70 nm)
1-7. Catalyst / photopolymerization initiator (Irgacure 1173, manufactured by BASF)

(Production Example 1) Production of PEDOT: PSS aqueous dispersion Using a 2000 ml three-necked glass flask equipped with a cooling tube, 92.3 parts of polystyrenesulfonic acid aqueous solution (manufactured by Akzo Nobel, VERSA-TL72) and 3,4-ethylene 7.1 parts of dioxythiophene (EDOT) was added to 1000 parts of ion-exchanged water to obtain a mixed solution. While stirring this mixed solution, a solution prepared by dissolving 4.0 parts of ferric sulfate and 14.8 parts of ammonium peroxodisulfate in 100 parts of ion-exchanged water was added and stirred at 20 ° C. for 24 hours for oxidation polymerization. Went. Next, 15% by weight of a cation exchange resin (manufactured by Organo Corporation, Amberlite IR120B) and an anion exchange resin (manufactured by Organo Corporation, Amberlite IRA67) were added, and the mixture was further stirred for 18 hours. The obtained reaction mixture was filtered with a glass filter, then homogenized with a high pressure homogenizer 10 times at 100 MPa, and then 5% by weight of dimethyl sulfoxide was added to obtain a PEDOT: PSS aqueous dispersion. .

(Production Example 2) Production of aqueous dispersion of carbon nanotubes 1 part by weight of carbon nanotubes (Zeon Nanotechnology Co., Ltd., ZEONANO SG101) having an average length of 300 μm and a diameter of about 4 nm, sodium dodecylbenzenesulfonate (Wako Pure Chemical Industries, Ltd.) as a dispersant 10 parts by weight) and 989 parts by weight of pure water are placed in a glass beaker, dispersed with an ultrasonic homogenizer at 40 W for 30 minutes, and then undispersed carbon nanotubes are removed with a centrifuge 3500 rpm. Thus, a carbon nanotube dispersion having a solid content of 1.1% by weight was obtained.

(Production Example 3) Preparation of acrylic resin film Acrylic resin (Parapet HR-S, copolymer monomer weight ratio = methyl methacrylate / methyl acrylate = 99/1, manufactured by Kuraray Co., Ltd.) 90 parts by weight and acrylonitrile-styrene Pellets with 10 parts by weight of resin (Toyo AS AS20, manufactured by Toyo Styrene Co., Ltd.) were supplied to a biaxial extruder and melt extruded into a sheet at about 280 ° C. to obtain films having a thickness of 160 μm and 400 μm.

2. Examples (Examples 1 to 13, Comparative Examples 3 to 5)
A conductive material, a thermoplastic resin, a thermosetting resin, a photocurable resin, a slip agent, fine particles, water, and propylene glycol were mixed so as to obtain a solid content shown in Table 1, thereby obtaining a resin composition. Here, the amount of propylene glycol was added so as to be 2% by weight in the coating solution. Moreover, pH was adjusted by adding ammonia water made by Tokyo Chemical Industry Co., Ltd. About the obtained resin composition, pH, solid content rate, and liquid stability were calculated | required with the following method.
In addition, a transparent conductive laminate having a transparent conductive film is applied on the thermoplastic resin substrate prepared in Production Example 3 using a bar coating method and dried at 70 ° C. for 5 minutes using a blow dryer. The surface resistivity and curl properties were measured and evaluated. Further cut into 20 cm × 20 cm, fixed on the stage, heated to 140 ° C., stretched to 20 cm × 50 cm, stretched 2.5 times, stretched to 40 cm × 40 cm, stretched 4 ×, 40 cm × Stretching to 60 cm performs 6-fold stretching, and stretching to 60 cm x 60 cm performs 9-fold stretching. For the transparent conductive film after stretching, the coefficient of friction, scratch resistance, stretchability, conductivity, curl properties Evaluated.
Here, what contained a photocurable resin was hardened by irradiating with an ultraviolet ray of 500 mJ / cm ² using a metal halide lamp after drying at 70 ° C. for 5 minutes. The results are shown in Table 1.

(Example 14, Comparative Examples 1-2)
A conductive material, a thermoplastic resin, a thermosetting resin, a photocurable resin, a slip agent, fine particles, water, and propylene glycol were mixed so as to obtain a solid content shown in Table 1, thereby obtaining a resin composition. Here, the amount of propylene glycol was added so as to be 2% by weight in the coating solution. Moreover, pH was adjusted by adding ammonia water made by Tokyo Chemical Industry Co., Ltd. About the obtained resin composition, pH, solid content rate, and liquid stability were calculated | required with the following method.

Transparent conductive film having a transparent conductive film by applying the resin composition on the thermoplastic resin substrate produced in Production Example 3 using a bar coating method and drying at 70 ° C. for 5 minutes using a blow dryer. A laminate was produced. Next, on the thermoplastic resin substrate opposite to the transparent conductive film, epoxy resin is added to 100 parts by weight of urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 210, solid content 33%) using a bar coating method. A composition for forming an easy-adhesion layer in which 1 part by weight of a crosslinking agent (manufactured by Nagase ChemteX Corporation, Denacol EX-810, solid content rate 100%) and 100 parts by weight of pure water were mixed and dried at 70 ° C. for 5 minutes. As a result, a back layer having an easy adhesion function was formed.

After measuring and evaluating the surface resistivity and curl properties, the sheet was further cut to 20 cm × 20 cm, fixed on the stage, heated to 140 ° C., and stretched to 40 cm × 40 cm, and then stretched 4 times. The transparent conductive film was evaluated for friction coefficient, scratch resistance, stretchability, conductivity, and curling property.
The results are shown in Table 1.

(Example 15)
The composition for forming an easy-adhesion layer was obtained by adding 60 parts by weight of an oxetane compound (manufactured by Toagosei Co., Ltd., OXT-221) and 40 parts by weight of an epoxy compound (manufactured by Mitsubishi Chemical Corporation, YL6753), a photocationic polymerization initiator (manufactured by ADEKA) SP-170) Evaluation was conducted in the same manner as in Example 14 except that the composition was changed to a composition for forming an ultraviolet curable adhesive layer mixed with 3 parts by weight, and the results are shown in Table 1.

(Example 16)
A conductive material, a thermoplastic resin, a thermosetting resin, a photocurable resin, a slip agent, fine particles, water, and propylene glycol were mixed so as to obtain a solid content shown in Table 1, thereby obtaining a resin composition. Here, the amount of propylene glycol was added so as to be 2% by weight in the coating solution. Moreover, pH was adjusted by adding ammonia water made by Tokyo Chemical Industry Co., Ltd. About the obtained resin composition, pH, solid content rate, and liquid stability were calculated | required with the following method.

Transparent conductive film having a transparent conductive film by applying the resin composition on the thermoplastic resin substrate produced in Production Example 3 using a bar coating method and drying at 70 ° C. for 5 minutes using a blow dryer. A laminate was produced. Next, on the thermoplastic resin substrate opposite to the transparent conductive film, epoxy-based crosslinking is performed on 400 parts by weight of acrylic resin (manufactured by Soken Chemical Co., Ltd., SK Dyne 2094, solid content: 25%) using a bar coating method. An adhesive layer forming composition mixed with 1 part by weight of an agent (trade name “E-AX”, manufactured by Soken Chemical Co., Ltd.) is applied and dried at 70 ° C. for 5 minutes to form a back layer having an adhesive function. did.

After measuring and evaluating the surface resistivity and curling property, it was further cut into 20 cm × 20 cm, fixed on the stage, heated to 140 ° C., and stretched to 40 cm × 40 cm, and then stretched to 40 cm × 60 cm. The film was stretched to perform a 6-fold stretching process, and the transparent conductive film after the stretching process was evaluated for friction coefficient, scratch resistance, stretchability, conductivity, and curling property.
The results are shown in Table 1.

3. Evaluation method (pH)
It measured using the pH meter (Horiba, Ltd. make, F-55) on 25 degreeC conditions.

(Solid content rate)
The weight of the resin composition obtained in each Example and Comparative Example and the weight after the resin composition was heated and dried at 120 ° C. for 2 hours in a blowing oven were weighed, and the solid content ratio was calculated based on the following formula: Calculated.

Solid content (%) = weight of resin composition after drying / weight of resin composition before drying

(Liquid stability)
The resin composition immediately after production was put in a thermostatic bath and kept at 25 ° C., and the liquid state of the resin composition after standing for 200 hours was visually observed and evaluated according to the following criteria.
A: No precipitate is observed.
○: Slight precipitate is observed.
X: A precipitate is observed.

(Conductivity)
By adjusting the wire bar on the thermoplastic resin substrate having the thickness shown in Table 1, a transparent conductive laminate having a film thickness before drawing as shown in Table 1 was obtained. The obtained transparent conductive laminate was stretched at a magnification as shown in Table 1, and then the surface resistivity of the transparent conductive film was determined by Loresta GP MCP-T600 manufactured by Mitsubishi Chemical Corporation, and evaluated according to the following criteria.
◎: Surface resistivity is 10 ⁸ Ω / □ or less ○: Surface resistivity is less than 10 ¹³ Ω / □ ×: Surface resistivity is 10 ¹³ Ω / □ or more

(Curl property)
By adjusting the wire bar on the thermoplastic resin substrate having the thickness shown in Table 1, a transparent conductive laminate having a film thickness before drawing as shown in Table 1 was obtained. Check whether the transparent conductive laminate before stretching and the transparent conductive laminate cut into a 20 cm × 20 cm size and the transparent conductive laminate cut into a 20 cm × 20 cm size are visually curled after stretching at the magnification described in Table 1. And evaluated according to the following criteria.
A: No curling after stretching and before stretching ○: No curling only before stretching ×: Curling after stretching and before stretching

(Coefficient of friction)
By adjusting and applying a wire bar on a 160 μm thick thermoplastic resin substrate, a transparent conductive laminate having a film thickness of 0.2 μm after the 4-fold stretching was obtained. The obtained transparent conductive film was measured with an automatic horizontal servo stand (manufactured by Nippon Measurement System Co., Ltd., JSH-H1000) based on the friction coefficient test method of JIS K7125, and evaluated according to the following criteria.
At this time, a commercially available acrylic base material (manufactured by Sumitomo Chemical Co., Ltd., Technoloy S014G, 75 μm thickness) was attached to the bottom surface of the sliding piece using a double-sided tape having a thickness of 1 mm and pulled at a speed of 10 mm / min.
・ Static friction coefficient ◎: Static friction coefficient 0.4 or less ○: Static friction coefficient 0.4 exceeding 0.8 or less △: Static friction coefficient 0.8 exceeding 1.5 or less ×: Static friction coefficient 1.5 exceeding or Starting to move after one side of the sliding piece is lifted: Coefficient of dynamic friction ◎: Coefficient of dynamic friction of 0.3 or less ○: Coefficient of dynamic friction exceeding 0.3 or less 0.6 or less Δ: Coefficient of dynamic friction exceeding 0.6 0 or less x: The coefficient of dynamic friction exceeds 1.0 or the sliding piece moves while causing obvious vibration

(Stretch resistance: surface resistivity)
The transparent conductive laminated body whose film thickness of the transparent conductive film before an extending | stretching process is 0.4 micrometer was obtained by adjusting and apply | coating a wire bar on the thermoplastic resin base material of 160 micrometers in thickness. The surface resistivity was measured by Loresta GP MCP-T600 manufactured by Mitsubishi Chemical Corporation, and the surface resistivity increase ratio before and after 4-fold stretching was calculated according to the following formula and evaluated according to the following criteria.

Surface resistivity after stretching (Ω / □) ÷ Surface resistivity before stretching (Ω / □)

A: Surface resistivity increase ratio is 10 times or less. O: Surface resistivity increase ratio exceeds 10 times and 100 times or less. Δ: Surface resistivity increase ratio exceeds 100 times and 1000 times or less. X: Surface resistivity increase ratio. Exceeds 1000 times

(Stretch resistance: Haze)
The transparent conductive laminated body whose film thickness of the transparent conductive film before an extending | stretching process is 0.4 micrometer was obtained by adjusting and apply | coating a wire bar on the thermoplastic resin base material of 160 micrometers in thickness. The haze was measured using a haze computer HGM-2B manufactured by Suga Test Instruments Co., Ltd. At the same time, the uncoated acrylic film was subjected to the same stretching process, and the haze increase ratio before and after the 4-fold stretching process was calculated according to the following formula and evaluated according to the following criteria.

(Haze after transparent conductive laminate stretching process−Haze after uncoated substrate stretching process) ÷ (Haze before transparent conductive laminate stretching process—Haze before uncoated substrate stretching process)

◎: Haze increase ratio is 1 or less ○: Haze increase ratio exceeds 1 time to 2 times or less △: Haze increase ratio exceeds 2 times to 3 times or less ×: Haze increase ratio exceeds 3 times

(Abrasion resistance)
The thickness of the film after drying is as shown in Table 1 by adjusting the wire bar on the thermoplastic resin substrate having the thickness shown in Table 1 and performing stretching at the magnification as shown in Table 1. A transparent conductive laminate was obtained. The scratch resistance of the obtained transparent conductive film was evaluated with a Gakushin type dyeing friction fastness tester (manufactured by Yasuda Seiki Seisakusho, flat type). A non-woven fabric (Bencott, manufactured by Asahi Kasei Co., Ltd.) is attached to the friction piece of the Gakushoku Dyeing Friction Fastness Tester, rubbing 10 times while applying a load of 500 g, and visually checking the surface state of the transparent conductive film. Evaluation was based on criteria.
A: No scratches are observed. O: About 10 scratches are observed. Δ: About 20 scratches are observed. X: 30 or more scratches are observed, or the transparent conductive film is peeled off.

Claims (12)

60 to 97.9 wt% of the thermoplastic resin (a), 1 to 30 wt% of the conductive material (b), 0.1 to 10 wt% of fine particles (c) having an average particle size of 10 to 500 nm, and A transparent conductive film for surface protection comprising 1 to 20% by weight of a slip agent (d),
It is for use in a drawing process to make the film thickness 0.2 μm or less by stretching 2.5 to 9 times,
A transparent conductive film having a static friction coefficient and a dynamic friction coefficient of 1.5 or less and 1.0 or less, respectively, when the film thickness is 0.2 μm by a stretching process by 4 times stretching. The transparent conductive film according to claim 1, wherein the thermoplastic resin (a) is at least one selected from the group consisting of an ester resin, a urethane resin, an acrylic resin, and a polyether resin. The transparent conductive film according to claim 1 or 2, wherein the conductive agent (b) is a conductive polymer and / or a carbon nanomaterial. The transparent conductive film according to any one of claims 1 to 3 , wherein the fine particles (c) are inorganic fine particles and / or organic fine particles having a crosslinked structure. The transparent conductive film according to any one of claims 1 to 4, wherein the slip agent (d) is a silicone resin and / or a fluorine resin. The transparent conductive laminated body by which the transparent conductive film of any one of Claims 1-5 was arrange | positioned on the base material. The transparent conductive laminate according to claim 6, wherein the substrate is a thermoplastic resin substrate. The transparent conductive laminate according to claim 6 or 7, further comprising an acrylic adhesive layer and / or a urethane-based easy adhesion layer. The transparent conductive laminated body of Claim 8 arrange | positioned in order of the transparent conductive film of any one of Claims 1-5, a base material, an acrylic adhesive layer, and / or a urethane type easily bonding layer. A three-dimensional display comprising the transparent conductive laminate according to any one of claims 6 to 9. 60 to 97.9 wt% of the thermoplastic resin (a), 1 to 30 wt% of the conductive material (b), 0.1 to 10 wt% of fine particles (c) having an average particle size of 10 to 500 nm, and The resin composition for forming the transparent conductive film of any one of Claims 1-5 containing 1 to 20 weight% of slip agents (d). Water or water-alcohol as a solvent (f) together with a thermoplastic resin (a), a conductive material (b), fine particles (c) having an average particle diameter of 10 to 500 nm, and a solid content containing a slip agent (d) Including a mixed solvent, solid content is 10% or less, pH is 4-10 ,
In the solid content, the thermoplastic resin (a) is 60 to 97.9% by weight, the conductive material (b) is 1 to 30% by weight, the fine particles (c) is 0.1 to 10% by weight, and the slip agent (d The resin composition for forming the transparent conductive film of any one of Claims 1-5 containing 1-20 weight% .