JP2007253425A - Conductive film for transfer and object with transparent conductive layer using this film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive film for transfer for forming a uniform-thickness transparent conductive layer which has low electric resistance value on the surface of a targeted object and superior slidability/flexibility, and an object with the transparent conductive layer using the conductive film. <P>SOLUTION: This conductive film for transfer includes at least a support 1, the conductive layer 4, which is releasable from the support 1, formed on the support 1 and an adhesive layer 5 formed on the conductive layer 4. In addition, the conductive layer 4 is a high-density layer of a conductive fine particle, and the adhesive layer 5 is formed of an adhesive composition containing at least an ether compound with an active energy radiation reactive group and an ether bond. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a transfer conductive film and an object provided with a transparent conductive layer using the same.

  The transparent conductive layer can be used as a transparent electrode such as a plasma display panel electrode, an electroluminescence panel electrode, an electrochromic element electrode, a liquid crystal electrode, a transparent surface heating element, and a touch panel, and can be used as a transparent electromagnetic wave shielding film. it can.

  Currently, the transparent conductive film is mainly produced by a sputtering method. The sputtering method is excellent in that a conductive film having a low surface electric resistance can be formed even with a certain large area. However, there is a drawback that the apparatus is large and the film forming speed is slow.

  Attempts have also been made to produce a transparent conductive film by a coating method. In the conventional coating method, a conductive paint in which conductive fine particles are dispersed in a binder solution is applied onto a substrate, dried and cured, and a conductive film is formed. The coating method has an advantage that a conductive film having a large area can be easily formed, the apparatus is simple, the productivity is high, and the conductive film can be manufactured at a lower cost than the sputtering method. In the coating method, when conductive fine particles come into contact with each other, an electrical path is formed to develop conductivity. However, the conductive film produced by the conventional coating method has a drawback that the contact between the conductive fine particles is insufficient due to the presence of the binder, and the resulting conductive film has a high electric resistance value (inferior in conductivity). , Its use will be limited.

  As a coating method not using a binder resin, for example, JP-A-8-199096 discloses a binder comprising a tin-doped indium oxide (ITO) powder, a solvent, a coupling agent, a metal organic acid salt or an inorganic acid salt. A method of applying a conductive film-forming coating material not included on a glass plate and firing at a temperature of 300 ° C. or higher is disclosed. In this method, since no binder is used, the electric resistance value of the conductive film is lowered. However, firing at a high temperature is necessary, and the base material is limited to a material that can withstand high temperatures such as a glass plate.

  Japanese Patent Application Laid-Open No. 6-103839 discloses a method for producing a transparent conductive substrate by transfer.

  WO 01/87590 discloses a conductive film for transfer for forming a transparent conductive layer on the surface of a target object. The conductive layer of the transfer conductive film is formed by compressing conductive fine particles.

  WO 2005/022559 discloses a transfer conductive film for forming a transparent conductive layer on the surface of a target object. The conductive layer of the transfer conductive film is formed by compressing conductive fine particles, and the gap between the conductive fine particles is impregnated with an organic group-containing metal oxide to be converted into a conductive metal oxide. Yes. After the conductive layer is transferred onto the target object surface, the organic group-containing metal oxide is converted into a conductive metal oxide.

JP-A-8-199096 JP-A-6-103839 WO01 / 87590 WO2005 / 022559

  According to the study by the present inventors, for a transparent electrode application such as a touch panel (TTP), the transparent conductive layer needs to have excellent sliding properties on the surface and excellent flexibility. Here, the sliding property means that the surface electrical resistance value is kept low even when the surface of the transparent conductive layer is touched with a finger or rubbed with a pen. The term “flexibility” means that the surface electrical resistance value is kept low even after the transparent conductive layer is bent and returned to its original state. In the conventional transfer conductive film, the conductive layer is flexible before transfer to the target object, that is, before the adhesive layer is cured. However, it has been found that the flexibility of the conductive layer is insufficient after the transfer to the target object, that is, after the adhesive layer is cured.

  An object of the present invention is to provide a conductive film for transfer for forming a transparent conductive layer having a uniform thickness which has a low electrical resistance value on the surface of a target object and is excellent in sliding characteristics and flexibility. Another object of the present invention is to provide an object having a transparent conductive layer having a uniform thickness on the surface of the object, which has a low electrical resistance value and is excellent in sliding characteristics and flexibility.

  In the conductive film for transfer, the inventors include an ether compound having an active energy ray-reactive group and an ether bond in an adhesive layer provided on a conductive layer made of a compressed layer of conductive fine particles. Thus, it has been found that a transparent conductive layer having excellent sliding characteristics and flexibility can be obtained.

The present invention includes the following inventions.
(1) A conductive film for transfer comprising at least a support, a conductive layer that is peelable from the support on the support, and an adhesive layer on the conductive layer,
The conductive layer is a compressed layer of conductive fine particles,
The said adhesive bond layer is the electroconductive film for transfer currently formed from the adhesive composition containing at least the ether compound which has an active energy ray reactive group and an ether bond.

The compressed layer of conductive fine particles can be obtained by compressing a conductive fine particle-containing layer formed by applying and drying a liquid in which conductive fine particles are dispersed on a support. The compressed layer of conductive fine particles is preferably obtained by compressing with a compressive force of 44 N / mm ² or more.

  When the conductive film for transfer is produced, the conductive fine particle dispersion may contain a small amount of resin, but preferably does not contain a resin. In the case where the dispersion liquid of the conductive fine particles contains a resin, the content of the resin is preferably less than 25 when expressed in volume and the volume of the conductive fine particles is 100. When the conductive fine particle-containing layer is compressed, the resin is not contained, or even if it is contained in a small amount, the contact point between the conductive fine particles is increased after compression, and the film strength of the conductive layer is increased. As it increases, the conductivity becomes good.

  There is a gap between the conductive fine particles in the compressed layer of the conductive fine particles. This void is impregnated with the adhesive composition of the adhesive layer formed on the compression layer.

(2) The conductive film for transfer according to (1), wherein the ether compound has an ethylene oxide unit and / or a propylene oxide unit.

(3) In the adhesive layer, the ether compound is contained in an amount of 10 to 80 parts by weight with respect to 100 parts by weight (as a nonvolatile content) of the total amount of components other than the ether compound, The conductive film for transfer as described in (2).

(4) The conductive fine particles include indium oxide, tin-doped indium oxide (ITO), gallium-doped indium oxide, zinc-doped indium oxide, tin oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), and oxidation. Conductive inorganic fine particles selected from the group consisting of zinc, aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), fluorine-doped zinc oxide, indium-doped zinc oxide, boron-doped zinc oxide, and cadmium oxide, The conductive film for transfer according to any one of (1) to (3).

(5) An object having an adhesive layer on the surface and a transparent conductive layer having a transparent conductive layer on the adhesive layer,
The conductive layer is a compressed layer of conductive fine particles,
The adhesive layer is formed from an adhesive composition containing at least an ether compound having an active energy ray reactive group and an ether bond,
An object provided with a transparent conductive layer, wherein the conductive layer is impregnated with an adhesive composition.

  The object provided with such a transparent conductive layer is obtained by transferring the conductive layer of the transfer conductive film to the surface of the target object via the adhesive layer using the transfer conductive film of the present invention. be able to. The adhesive composition constituting the adhesive layer contains an ether compound, and a part of the adhesive composition impregnated in the conductive layer is present in the surface layer portion of the transparent conductive layer. Therefore, the transparent conductive layer has excellent surface sliding properties and excellent flexibility.

  In the present invention, “a conductive layer that can be peeled from the support” or “a conductive layer that can be peeled from the support” means that the support and the conductive layer can be peeled from each other. When the conductive film for transfer of the present invention is actually used, the support is often peeled off from the conductive layer attached on the surface of the target object via the adhesive layer.

  In the transfer conductive film of the present invention, it is also preferable to have an intermediate layer between the support and the conductive layer in order to facilitate the peeling of the conductive layer from the support during transfer.

  In the present invention, the transferred conductive layer may be patterned.

  ADVANTAGE OF THE INVENTION According to this invention, the electroconductive film for transfer for forming the transparent conductive layer of the uniform thickness which has the low electrical resistance value on the surface of a target object and is excellent in a sliding characteristic and a flexibility is provided. This conductive film for transfer can be produced by a simple operation of applying a dispersion of conductive fine particles, forming a compressed layer of conductive fine particles by compression, and then applying and forming an adhesive layer.

  By using the conductive film for transfer of the present invention, by transferring the conductive layer of the conductive film for transfer to the surface of the target object via the adhesive layer, the surface of the target object is excellent in surface sliding characteristics, A transparent conductive layer having excellent flexibility can be formed.

  First, the conductive film for transfer of the present invention (hereinafter also simply referred to as a conductive film) will be described.

  FIG. 1 is a cross-sectional view showing a layer configuration example of a transfer conductive film. In the conductive film of FIG. 1, a base layer (3) is formed on the support (1), a transparent conductive layer (4) is formed on the base layer (3), and an adhesive is formed on the transparent conductive layer (4). An agent layer (5) is formed. The transparent conductive layer (4) comprises a compressed layer of conductive fine particles, and is provided so as to be peelable from the support (1). In order to protect the adhesive layer surface until use, a release film (not shown) may be provided on the adhesive layer (5).

  The term “transparent” in the present invention means that visible light is transmitted, and even if light is scattered to some extent, it is included in the concept of transparency. The level of light scattering differs depending on the application of the conductive film for transfer, i.e., the application of the target object on which the conductive layer is transferred, and it is transparent even in the case of light scattering, which is generally said to be translucent. Included in the concept.

  In the present invention, as the support (1), a flexible resin film that does not crack even when the compression force in the compression step described later is increased is suitable. In the present invention, in the production of the conductive film for transfer, since there is no pressurizing step or baking step at high temperature, a resin film can be used as a support. Examples of the resin film include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films such as polyethylene and polypropylene, polycarbonate films, acrylic films, and norbornene films.

  The underlayer (3) preferably has a certain degree of hardness and cushioning properties in order to form and hold the conductive layer (4) composed of a compressed layer of conductive fine particles on the support, On the other hand, since the base layer (3) and the conductive layer (4) are peeled off during the transfer, the base layer (3) is preferably relatively hard, and the support (1) and the base layer (3 ) Is preferably higher than the adhesion between the base layer (3) and the conductive layer (4). The underlayer (3) is preferably selected from silicone resin, acrylic resin, urethane resin, vinyl chloride resin, etc., and a resin solution is applied on the support (1) and dried. Application | coating in this case can be performed by a well-known method. For example, it can be performed by a coating method such as an extrusion nozzle method, a blade method, a knife method, a bar coating method, a kiss coating method, a gravure roll method, a dipping method, a reverse roll method, a direct roll method, a curtain method, or a squeeze method. The thickness of the underlayer (3) is not limited, but may be, for example, about 0.5 to 20 μm.

  A transparent conductive layer (4) is formed on the underlayer (3) using a dispersion of conductive fine particles. Examples of the conductive fine particles include indium oxide, tin-doped indium oxide (ITO), gallium-doped indium oxide, zinc-doped indium oxide, tin oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), and zinc oxide. Conductive inorganic fine particles such as aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), fluorine-doped zinc oxide, indium-doped zinc oxide, boron-doped zinc oxide, and cadmium oxide are used. ITO is preferable in that it provides better conductivity. Or what coated inorganic material, such as ATO and ITO, on the surface of fine particles which have transparency, such as barium sulfate, can also be used. The particle diameter of these fine particles varies depending on the degree of light scattering required depending on the use of the conductive layer, and cannot generally be said depending on the shape of the particles, but is generally 1.0 μm or less, and 5 nm to 100 nm. Preferably, 5 nm to 80 nm is more preferable. Moreover, you may use the particle | grains surface-treated with the silane coupling agent.

  The dispersion medium for dispersing the conductive fine particles is not particularly limited, and various known liquids can be used. For example, as liquid, saturated hydrocarbons such as hexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, diisobutyl ketone, etc. Ketones, esters such as ethyl acetate and butyl acetate, ethers such as tetrahydrofuran, dioxane and diethyl ether, amides such as N, N-dimethylformamide, N-methylpyrrolidone (NMP) and N, N-dimethylacetamide And halogenated hydrocarbons such as ethylene chloride and chlorobenzene. Among these, polar liquids are preferable, and those having an affinity for water, such as alcohols such as methanol and ethanol, and amides such as NMP, have good dispersibility without using a dispersant. It is preferable. These liquids can be used singly or as a mixture of two or more. Moreover, a dispersing agent can also be used according to the kind of liquid.

  Water can also be used as a dispersion medium. When water is used, the surface of the support (1) (when there is no base layer) or the base layer (3) provided on the support needs to be hydrophilic. Since the resin film and the base resin layer are usually hydrophobic, water is easily repelled and it is difficult to obtain a uniform film. In such a case, it is necessary to mix alcohol with water, or to make the surface of the base resin layer hydrophilic by corona treatment or the like.

  The amount of the dispersion medium to be used is not particularly limited, and the dispersion liquid of fine particles may have a viscosity suitable for coating. For example, the amount of the liquid is about 100 to 100,000 parts by weight with respect to 100 parts by weight of the fine particles. It may be appropriately selected according to the kind of the fine particles and the dispersion medium.

  The fine particles may be dispersed in a dispersion medium by a known dispersion method. For example, it is dispersed by a sand grinder mill method. In dispersing, it is also preferable to use media such as zirconia beads in order to loosen the aggregation of the fine particles.

  The prepared dispersion of conductive fine particles is applied and dried on the support (1) (when there is no base layer) or the base layer (3) provided on the support to form a conductive fine particle-containing layer. . The application of the fine particle dispersion is not particularly limited, and can be performed by a known method. For example, the fine particle dispersion can be performed by a coating method similar to the method described in the application of the underlayer. The drying temperature depends on the type of dispersion medium used for dispersion, but is preferably about 10 to 150 ° C. If it is less than 10 ° C, condensation of moisture in the air tends to occur, and if it exceeds 150 ° C, the resin film support is deformed.

Thereafter, the conductive fine particle-containing layer is compressed by a sheet press, a roll press or the like to form a compressed layer of conductive fine particles. By compressing, the contact points between the conductive fine particles increase and the contact surface increases. For this reason, the coating strength increases and the electrical resistance value decreases. Excellent in conductivity, in order to obtain a conductive layer excellent in film strength, compression is preferably carried out at 44N / mm ² or more compression strength, 135N / mm ² or more compressive force and more preferably, the compression of 180 N / mm ² Force is more preferred. Since the pressure resistance of the apparatus has to be increased as the compressive force is increased, generally a compressive force of up to 1000 N / mm ² is appropriate.

  Thus, a transparent conductive layer (4) composed of a compressed layer of conductive fine particles is formed. The thickness of the conductive fine particle compressed layer may be about 0.1 to 10 μm, although it depends on the application. Moreover, in order to obtain a thick compressed layer of about 10 μm, a series of operations of applying a dispersion of fine particles, drying, and compression may be repeated.

  Next, an adhesive layer (5) made of an adhesive composition is formed on the transparent conductive layer (4). Since there is a gap between the conductive fine particles in the compressed layer of the obtained conductive fine particles, the adhesive composition is impregnated in the compressed layer.

  In the present invention, an ether compound (E) having an active energy ray-reactive group and an ether bond is included as an essential component, and a curable component (C) other than the ether compound (E) is included. An adhesive composition is used which has affinity for both the conductive layer (4) and the surface of the object to be transferred and can strongly bond both. For example, the adhesive composition includes an ether compound (E) having an active energy ray reactive group and an ether bond, a polymer resin (P), and a curable component (C) other than the ether compound (E) ( For example, an acrylic monomer (M)) and preferably a photopolymerization initiator are included.

  By adjusting the viscosity by using a combination of the polymer resin (P) component and the curable component (C) (for example, acrylic monomer (M)), while having adhesiveness, it is irradiated with active energy rays such as ultraviolet rays. An adhesive layer that becomes a cured product can be easily formed. What is necessary is just to have moderate adhesiveness.

  Examples of the polymer resin (P) include acrylic resins, silicone resins, epoxy resins, urethane resins, and cellulose resins. A publicly known thing can be used as acrylic resin, for example, acrylic resin 103B, 1BR-305 (all are the Taisei Kako Co., Ltd. product) etc. are mentioned.

  The curable component (C) is other than the ether compound (E), and is a compound having an active energy ray reactive group such as a (meth) acryloyl group or a vinyl group. In order to obtain sufficient hardness of the adhesive composition after curing, the curable component is a polyfunctional monomer or oligomer containing two or more, preferably three or more active energy ray reactive groups in one molecule. It is preferable to include.

  The curable component (C) preferably contains an acrylic monomer (M). Specific examples of the acrylic monomer (M) include 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, 3- (meth) acryloyloxyglycerin mono (meth) ) Acrylate and the like, but not necessarily limited thereto. Moreover, urethane acrylate, epoxy acrylate, etc. are also mentioned.

  As the acrylic monomer (M), known ones can be used. For example, trifunctional or higher acrylics such as KAYARAD GPO-303, KAYARAD TMPTA, and KAYARAD THE-330 (all manufactured by Nippon Kayaku Co., Ltd.). Based monomers.

  Moreover, you may use the compound which has a vinyl group as said sclerosing | hardenable component (C). Examples of the compound having a vinyl group include ethylene glycol divinyl ether, pentaerythritol divinyl ether, 1,6-hexanediol divinyl ether, trimethylolpropane divinyl ether, ethylene oxide-modified hydroquinone divinyl ether, ethylene oxide-modified bisphenol A divinyl ether, Examples include, but are not necessarily limited to, pentaerythritol trivinyl ether, dipentaerythritol hexavinyl ether, ditrimethylolpropane polyvinyl ether, and the like.

  The ether compound (E) having an active energy ray-reactive group and an ether bond improves the flexibility of the transparent conductive layer after transfer to the target object, and improves the sliding characteristics of the surface of the transparent conductive layer Contained.

The ether compound (E) includes an active energy ray reactive group such as a (meth) acryloyl group and a vinyl group, an ethylene oxide unit- [C ₂ H ₄ O]-, and a propylene oxide unit- [C ₃ H ₆ O]. And an alkylene oxide unit such as a tetramethylene oxide unit-[CH ₂ CH ₂ CH ₂ CH ₂ O]-. The alkylene oxide unit in the ether compound may be linear or branched. The number of alkylene oxide units contained in one molecule is better to some extent. For example, about 3-30 is good and about 5-20 is preferable.

  The presence of alkylene oxide units in the adhesive composition impregnated in the compressed layer is considered to provide a certain degree of flexibility in the cured adhesive composition. Therefore, the adhesive composition impregnated in the transparent conductive layer improves the flexibility of the transparent conductive layer even after transfer to the target object, and the adhesive exists near the surface of the transparent conductive layer after transfer to the target object. The composition is considered to improve the sliding characteristics on the surface of the transparent conductive layer.

  The ether compound (E) may be monofunctional (for example, ether bond-containing (meth) acrylate) or polyfunctional (for example, ether) for immobilization in an adhesive composition. It may be a bond-containing di (meth) acrylate, an ether bond-containing multi (meth) acrylate such as an ether bond-containing tri (meth) acrylate).

  The ether compound (E) is not particularly limited, and various compounds can be used. Specific examples of the compound include A-1206PE (ethoxylated polypropylene glycol # 700 diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) and APG700 (polypropylene glycol # 700 diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.). A600 (polyethylene glycol # 600 diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), polytetramethylene glycol diacrylate (PTMG, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethoxyglycerin triacrylate (A-GLY3E, Shin-Nakamura) Chemical Industry Co., Ltd.).

A-1206PE
CH ₂ = CH-CO-O- (C ₂ H ₄ O) k- (C ₃ H ₆ O) m- (C ₂ H ₄ O) n-CO-CH = CH ₂
k + n≈6, m≈12

APG700
CH ₂ = CH-CO-O- (CH (CH ₃ ) CH ₂ O) m- (CH ₂ CH (CH ₃ ) O) n-CO-CH = CH ₂
m + n = 12

A600
CH ₂ = CH-CO-O- (C ₂ H ₄ O) n-CO-CH = CH ₂
n = 14

PTMG
CH ₂ = CH-CO-O- (CH ₂ CH ₂ CH ₂ CH ₂ O) n-CO-CH = CH ₂
n = 9

Ethoxyglycerin triacrylate
CH ₂ [(OC ₂ H ₄ ) k-OCO-CH = CH ₂ ] -CH [(OC ₂ H ₄ ) m-OCO-CH = CH ₂ ] -CH _2- (OC ₂ H ₄ ) n-OCO- CH = CH ₂
k + m + n = 3

  In the adhesive composition, the ether compound (E) is contained in an amount of 10 to 80 parts by weight with respect to 100 parts by weight (as a non-volatile content) of the total amount of components other than the ether compound (E). Is preferred. The ether compound (E) within this range improves the flexibility of the conductive layer and the sliding properties of the surface of the conductive layer even after transfer to the target object. When the ether compound (E) is less than 10 parts by weight, the effect of improving flexibility and sliding properties is small. When the amount of the ether compound (E) exceeds 80 parts by weight, it becomes easy to absorb moisture in the adhesive due to the hydrophilic nature of the ether bond, and the electrical resistance value of the conductive layer tends to increase under high temperature and high humidity.

  In the adhesive composition, depending on the mixing ratio of the polymer resin (P) and the curable component (C) (preferably acrylic monomer (M)), the viscosity, tackiness, and hardness after curing of the coating film are increased. Changes. When the amount of the polymer resin (P) increases, the viscosity of the adhesive composition increases. If the polymer resin (P) is in an appropriate ratio, good tackiness can be obtained, and the hardness after curing can be obtained as the curable component (C) (preferably acrylic monomer (M)) is increased. In consideration of these, the blending ratio of the polymer resin (P) and the curable component (C) may be determined as appropriate. When the acrylic monomer (M) is used as the curable component (C), The polymer resin (P) and the acrylic monomer (M) are preferably contained in a weight ratio P / M = 0/100 to 80/20 as a non-volatile content, and P / M = 1/99 to 50 / 50 is more preferable, and P / M = 2/98 to 30/70 is more preferable.

  The adhesive composition usually further contains a photopolymerization initiator. Various photopolymerization initiators can be used, and examples thereof include KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.). If the quantity of a photoinitiator shall be about 0.01-20 weight% with respect to the total (P + C) weight of the sclerosing | hardenable component (C) containing acrylic resin (P) and an acrylic monomer (M). Good. When the adhesive layer is cured by irradiation with active energy rays such as ultraviolet rays, productivity when the conductive film for transfer is adhered to the target object is increased. Moreover, you may use the well-known thing which added the photoinitiator to the acrylic monomer as a photoinitiator. As what added the photoinitiator to the acryl-type monomer, ultraviolet curable resin SD-318 (Dainippon Ink Chemical Co., Ltd. product), XNR5535 (Nagase Sangyo Co., Ltd. product), etc. are mentioned, for example.

  In the said adhesive composition, you may include additives and oligomers, such as a ultraviolet absorber and an infrared absorber, as needed.

  A release film may be provided on the adhesive layer (5) of the transfer conductive film of the present invention to protect the adhesive layer surface until use.

  The adhesive layer (5) can be formed by applying an adhesive composition solution onto the conductive layer (4) and drying. Application of the adhesive composition solution is not particularly limited, and can be performed by a known method. For example, the adhesive composition solution can be applied by the same application method as described in Application of the underlayer. Dry after application. Alternatively, the adhesive composition solution is applied onto a separately prepared release support that has been subjected to a release treatment, and dried to form an adhesive layer, and this adhesive layer on the release support and the support (1) The adhesive layer (5) may be provided on the conductive layer (4) by laminating and adhering (adhering) the upper conductive layer (4). In this case, simultaneously with the formation of the adhesive layer (5), a peeling support is provided on the adhesive layer, and the adhesive layer surface is protected until use.

  A part of the adhesive composition is impregnated in the conductive layer (4). The thickness of the adhesive layer depends on the tackiness of the adhesive, but may be about 0.1 μm to 20 μm before curing, preferably 0.5 μm to 10 μm, and more preferably 1.0 μm to 5 μm.

  As described above, the conductive film for transfer of the present invention can be produced.

Next, the object provided with the transparent conductive layer of the present invention will be described.
FIG. 2 is a cross-sectional view showing a layer configuration example of an object provided with a transparent conductive layer. In FIG. 2, a transparent conductive layer (4) composed of a compressed layer of conductive fine particles is provided on the surface of an object (6) via an adhesive layer (5).

  The target object (6) is not particularly limited, and other than a flexible sheet or film, for example, a plate-like object or support that is difficult to form a coating layer having a uniform thickness Included are objects such as glass, ceramics, and metal that are difficult to directly form a compression layer. For example, various displays such as a touch panel are given as specific examples of the target object in the present invention.

  In order to obtain an object provided with the transparent conductive layer of the present invention, first, the conductive layer (4) of the above-mentioned transfer conductive film is transferred from the support (1) onto the target object (6). That is, the conductive film is attached to the surface of the target object (6) via the adhesive layer (5) of the conductive film so that the support (1) is on the outside, and the adhesive layer (5 ) Is preferably cured by ultraviolet irradiation, and then the support (1) of the conductive film is peeled off. In addition, the same adhesive as the adhesive layer (5) may be applied on the surface of the target object (6) in advance. When the conductive film support (1) is peeled after the adhesive layer (5) is cured, peeling occurs between the base layer (3) and the conductive layer (4) during transfer. The surface of the transparent conductive layer (4) is exposed.

  The adhesive composition constituting the adhesive layer (5) contains an ether compound. A part of the adhesive composition is impregnated in the transparent conductive layer (4). The flexibility of the transparent conductive layer (4) after curing is improved by the adhesive composition impregnated in the transparent conductive layer (4). A part of the adhesive composition impregnated in the transparent conductive layer (4) is present in the surface layer portion of the transparent conductive layer (4). Therefore, the transparent conductive layer (4) is also excellent in surface sliding characteristics.

  When transferring the conductive layer, the transfer target object may be surface-treated in advance. For example, when the object to be transferred is glass, the surface may be surface-treated with a silane coupling agent or the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[Example 1]
As shown in FIG. 1, a conductive film for transfer having a base resin layer (3), a transparent conductive layer (4) and a photosensitive adhesive layer (5) in this order on a support (1) in the following procedure. Created with.

(Formation of base resin layer)
Silicone resin was used for the hard base resin layer. 100 parts by weight of A solution and 300 parts by weight of B solution of silicone resin solution Fresella N-180 (manufactured by Matsushita Electric Works) were mixed to obtain a coating solution for the resin layer. One side of a 75 μm thick PET film (1) (HSL, manufactured by Teijin DuPont Film) was subjected to corona treatment. The coating solution was applied to the corona-treated surface of the PET film (1), dried, and cured at 70 ° C. for 24 hours to form a 0.7 μm-thick silicone resin layer (3).

(Formation of transparent conductive layer)
300 parts by weight of ethanol was added to 100 parts by weight of ITO fine particles SUFP-HX (manufactured by Sumitomo Metal Mining Co., Ltd.) having a primary particle diameter of 20 nm, and the media was dispersed as zirconia beads with a disperser. The obtained coating liquid was applied onto the resin layer (3) using a bar coater, and dried by sending hot air of 50 ° C. The obtained film is called an ITO film before compression. The thickness of the ITO-containing coating film was 1.7 μm.

First, a preliminary experiment for confirming the compression pressure was performed.
Using a roll press machine equipped with a pair of metal rolls having a diameter of 140 mm (the roll surface is subjected to hard chrome plating), the roll is not rotated and the roll is heated to room temperature (23 ° C.) without heating. The ITO film before compression was sandwiched and compressed. At this time, the pressure per unit length in the film width direction was 660 N / mm. Next, when the pressure was released and the length of the compressed portion in the longitudinal direction of the film was examined, it was 1.9 mm. From this result, it was compressed at a pressure of 347 N / mm ² per unit area.

  Next, the ITO film before compression similar to that used in the preliminary experiment was sandwiched between metal rolls and compressed at a pressure of 660 N / mm, and the roll was rotated and compressed at a feed rate of 5 m / min. In this way, a film having an ITO layer compressed on the hard base resin layer (3) (referred to as a compressed ITO film) was obtained. The thickness of the ITO compressed layer (4) was 1.0 μm.

(Formation of photosensitive adhesive layer)
100 parts by weight of acrylic resin 1BR-305 (solid content: 39.5% by weight, manufactured by Taisei Kako Co., Ltd.), 117 parts by weight of UV curable resin liquid XNR5535 (manufactured by Nagase Sangyo Co., Ltd.), UV curing containing ethylene oxide 39 parts by weight of type resin liquid A-1206PE (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 246 parts by weight of methyl ethyl ketone were added to obtain an adhesive layer coating solution.
First, an adhesive layer coating solution was applied to a silicone-treated release PET film S314 (manufactured by Toray Industries, Inc.) and dried to form an 8 μm thick adhesive layer on the release PET film.
Next, the film on which the ITO compressed layer (4) was formed and the peeled PET film on which the adhesive layer was formed were laminated so that the ITO compressed layer (4) and the adhesive layer were in contact with each other. In this way, an adhesive layer (5) was formed on the ITO compression layer (4) to obtain a conductive film for transfer.

(Applying transparent conductive layer to PET film by transfer)
By peeling off the silicone release PET film S314 of the obtained conductive film for transfer, the adhesive layer (5) is exposed, and a laminator is used so that the adhesive layer (5) is in contact with the 188 μm thick PET film (6). Pasted. The adhesive layer (5) was cured by irradiating with ultraviolet rays. Thereafter, the support PET film (1) was peeled off. The adhesion between the silicone resin layer (3) and the support (1) is higher than the adhesion between the silicone resin layer (3) and the ITO compression layer (4), and the silicone resin layer (3) ) Was peeled off. An exposed ITO compressed layer (4) was formed on the PET film (6). As shown in FIG. 2, an ITO compression layer (4) was applied on the PET film (6) via an adhesive layer (5). Thus, a conductive PET film provided with an ITO transparent conductive layer was obtained.

(Production of touch panel)
A touch panel was prepared by using a PET film provided with an ITO transparent conductive layer as an upper electrode and glass ITO printed with a dot spacer as a lower electrode, facing each other.

[Example 2]
39 parts by weight of A-1206PE (manufactured by Shin-Nakamura Chemical Co., Ltd.) in the adhesive layer coating solution was changed to 39 parts by weight of propylene oxide-containing UV curable resin liquid APG700 (manufactured by Shin-Nakamura Chemical Co., Ltd.). Except for the above, a transfer conductive film was obtained in the same manner as in Example 1. Using the obtained transfer conductive film, a transparent conductive layer was applied to the PET film in the same manner as in Example 1 to obtain a conductive PET film. And the touch panel was produced.

[Example 3]
39 parts by weight of A-1206PE (manufactured by Shin-Nakamura Chemical Co., Ltd.) in the adhesive layer coating solution was changed to 39 parts by weight of ethylene oxide-containing UV curable resin liquid A600 (manufactured by Shin-Nakamura Chemical Co., Ltd.). Except for the above, a transfer conductive film was obtained in the same manner as in Example 1. Using the obtained transfer conductive film, a transparent conductive layer was applied to the PET film in the same manner as in Example 1 to obtain a conductive PET film. And the touch panel was produced.

[Comparative Example 1]
Acrylic resin 1BR-305 (solid content: 39.5% by weight, manufactured by Taisei Kako Co., Ltd.) 100 parts by weight, UV curable resin liquid XNR5535 (manufactured by Nagase Sangyo Co., Ltd.) 156 parts by weight, and methyl ethyl ketone 246 parts by weight Was added to obtain an adhesive layer coating solution.
A conductive film for transfer was obtained in the same manner as in Example 1 except that this adhesive layer coating solution was used. Using the obtained transfer conductive film, a transparent conductive layer was applied to the PET film in the same manner as in Example 1 to obtain a conductive PET film. And the touch panel was produced.

[Performance evaluation]
In the following manner, a bending test was performed on each conductive PET film, and a sliding test was performed on each touch panel.

(Bending test)
A silver electrode is wired on the produced conductive PET film so that the distance between the electrodes is 15 mm, and the conductive PET film is wound around a cylindrical rod of φ10 mm with the conductive layer on the outer side by 180 degrees, and the state Held for 10 seconds and then released. This bending operation was repeated 5 times. The electrical resistance value (Ω / □) of the transparent conductive layer surface was measured before the bending operation (initial stage) and after each bending operation.

(Sliding test)
In an atmosphere of a temperature of 20 ° C. and a relative humidity of 60%, the surface of the upper electrode of the manufactured touch panel is placed on the lower electrode side with a polyacetal touch pen formed into a spherical (hemispheric) pen tip. A sliding test is performed by reciprocating the pen tip in the pressed state, and the electrical resistance value (Ω / □) of the surface of the upper electrode before the sliding test (initial) and after the sliding test is measured by a resistance measuring device ( Measured by the 4-terminal method using Loresta EP, manufactured by Mitsubishi Chemical Corporation. In the sliding test, a load of 250 g was applied to the touch pen, and the number of reciprocations was 200,000 times.

  The obtained results are shown in Table 1. Table 1 shows each electric resistance value (Ω / □) and the rate of change of the electric resistance value based on the initial value.

  From Table 1, in Examples 1-3, all were excellent in the flexibility and the sliding characteristic. In Comparative Example 1, since the ether compound (E) was not contained in the adhesive layer coating solution, an increase in electrical resistance value was observed in the bending test and the sliding test.

It is sectional drawing which shows an example of the electroconductive film for transfer of this invention. It is sectional drawing which shows an example of the object to which the transparent conductive layer of this invention was provided.

Explanation of symbols

(1): Support
(3): Underlying resin layer
(4): Transparent conductive layer
(5): Adhesive layer
(6): Target object

Claims (5)

A conductive film for transfer comprising at least a support, a conductive layer that is peelable from the support on the support, and an adhesive layer on the conductive layer,
The conductive layer is a compressed layer of conductive fine particles,
The said adhesive bond layer is the electroconductive film for transfer currently formed from the adhesive composition containing at least the ether compound which has an active energy ray reactive group and an ether bond.   The conductive film for transfer according to claim 1, wherein the ether compound has an ethylene oxide unit and / or a propylene oxide unit.   The said ether compound in the said adhesive bond layer is 10-80 weight part with respect to 100 weight part (as a non volatile matter) of the total amount of components other than the said ether compound, The Claim 1 or 2 Conductive film for transfer.   The conductive fine particles include indium oxide, tin-doped indium oxide (ITO), gallium-doped indium oxide, zinc-doped indium oxide, tin oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), zinc oxide, and aluminum. Conductive inorganic fine particles selected from the group consisting of doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), fluorine-doped zinc oxide, indium-doped zinc oxide, boron-doped zinc oxide, and cadmium oxide. The conductive film for transfer according to any one of 3. An object having an adhesive layer on a surface and a transparent conductive layer having a transparent conductive layer on the adhesive layer,
The conductive layer is a compressed layer of conductive fine particles,
The adhesive layer is formed from an adhesive composition containing at least an ether compound having an active energy ray reactive group and an ether bond,
An object provided with a transparent conductive layer, wherein the conductive layer is impregnated with an adhesive composition.