TW201403635A - Conductive laminated body, patterned conductive laminated body, method for producing same, and touch panel using the same - Google Patents

Abstract

The present invention provides a patterned conductive laminated body which is excellent in the non-visibility of a pattern. A conductive laminated body which is the conductive laminated body having a conductive layer on at least one side of a substrate, characterizing by the conductive layer containing a metal linear structure with a network structure and any layer of the conductive layer body containing inorganic particles.

Description

Conductive laminate, patterned conductive laminate, method of manufacturing the same, and touch panel using same

The present invention relates to a conductive laminate and a patterned conductive laminate comprising a conductive region and a non-conductive region. More specifically, it relates to a highly non-recognizable patterned conductive laminate including a pattern portion of a conductive region and a non-conductive region. Further, the present invention relates to a patterned electrically conductive laminated body which can be used for a display element related to a liquid crystal display, an organic electroluminescence, an electronic paper, or the like, and an electrode element such as a solar cell module.

In recent years, conductive elements for electrodes such as touch panels, liquid crystal displays, organic electroluminescence, electronic paper, etc., and solar cell modules have been processed by forming non-conductive regions on conductive layers of conductive elements. It is used to form a desired pattern including a conductive region and a non-conductive region.

In the conductive layer, a conductive layer is laminated on the substrate. In addition to a conventional conductive film such as ITO or a metal thin film, a linear conductive component such as a metal nanowire is proposed. For example, there is a proposal to build a tree on a conductive layer with a metal nanowire as a conductive component. Conductive laminate of a lipid layer (Patent Document 1). Further, there has been proposed a conductive laminated body in which a metal nanowire is dispersed in a matrix having a high degree of hardening of a polyfunctional component (Patent Document 2). Further, it has been proposed to pattern a conductive laminate using a metal nanowire into a non-conductive region of a conductive region and a residual metal nanowire (Patent Document 3).

Further, when the conductive elements are applied to a touch panel or the like, it is necessary to form a wiring pattern, and as a pattern forming method, a chemical etching method using a photoresist and an etching liquid is generally used (Patent Document 4).

Advanced technical literature Patent literature

Patent Document 1 Japanese Patent Publication No. 2010-507199

Patent Document 2 Japanese Patent Laid-Open No. 2011-29037

Patent Document 3 Japanese Patent Laid-Open Publication No. 2010-140859

Patent Document 4 Japanese Patent Laid-Open Publication No. 2001-307567

However, in the conductive laminated system described in Patent Document 1, if a pattern including a conductive region and a non-conductive region is formed, a difference in the amount of the conductive component exists between the conductive region and the non-conductive region, and thus a difference in optical characteristics occurs. There is a problem that the pattern can be distinguished (that is, the non-recognition is low). In the method of improving the non-recognition of the pattern, the refractive index difference between the conductive laminated layer substrate and the conductive layer described in Patent Document 2 is reduced, and the conductive portion and the non-conductive region of the conductive laminated layer described in Patent Document 3 are electrically conductive. The difference in component residues is reduced, still There is a problem of low recognition of patterns. Moreover, as a pattern forming method of a conductive laminated body, the chemical etching method described in Patent Document 4 is generally used, and it is desired to improve the pattern non-recognition property by the patterning method.

The present invention has been made in view of the problems of the prior art, and a patterned electrically conductive laminated body having a high degree of non-recognition of a pattern portion is obtained.

In order to solve such a problem, the present invention adopts the following structure. that is,

(1) A conductive laminated body which is a conductive laminated body having a conductive layer on at least one side of a substrate, wherein the conductive layer comprises a metal-based linear structure having a network structure, and further any of the conductive laminated bodies The layer contains inorganic particles.

(2) The electrically conductive laminated body according to (1), wherein the substrate and the conductive layer have a layer containing inorganic particles.

(3) A patterned electrically conductive laminated body which is a patterned electrically conductive laminated body having a patterned conductive layer on at least one side of a substrate, wherein the patterned electrically conductive layer has a metal-based linear structure having a network structure The conductive region of the body and the non-conductive region in which the metal-based linear structure having the network structure is not present, and any layer of the laminated structure of the non-conductive region exists.

(4) The patterned conductive laminate according to (3), wherein the substrate and the patterned conductive layer have a layer having pores therebetween.

(5) The patterned electrically conductive laminated body according to (4) above, wherein the non-conductive region has a large number of voids compared to the conductive region.

(6) A method of producing a patterned conductive laminate, which is characterized by the method for producing a patterned conductive laminate according to any one of the above (3), (4), or (5), wherein The chemical treatment is performed to dissolve the inorganic particles described in the conductive laminate of (1) or (2) to form pores.

(7) The method for producing a patterned electrically conductive laminated body according to the above (6), wherein the inorganic particles are dissolved by a chemical treatment to form pores, and the metal-based linear structure having a network structure is also removed. Body, forming a non-conductive area.

(8) A patterned electrically conductive laminated body obtained by the method for producing a patterned electrically conductive laminated body according to (6) or (7) above.

(9) The electrically conductive laminated body according to (1) above, wherein the metal linear structure is a silver nanowire.

(10) The electrically conductive laminated body according to (1) above, wherein the inorganic particles have an average particle diameter of 500 nm or less.

The patterned conductive laminate according to any one of the above (3), (4), (5), or (8), wherein the non-conductive region contains pores having an average pore diameter of 500 nm. the following.

(12) The electrically conductive laminated body according to (1) above, wherein the inorganic particles are carbonates.

(13) A display body using the conductive laminated body according to (1) above, or the patterned conductive laminated body described in any one of the above (3), (4), (5), and (8) .

(14) A touch panel using the display body described in the above (13).

(15) An electronic paper using the display body described in the above (13).

According to the present invention, it is possible to provide a conductive laminated body in which the pattern portion is improved after the pattern is formed, and a patterned conductive laminated body in which the pattern portion is highly unrecognizable.

1‧‧‧Substrate

2‧‧‧ Conductive layer

3‧‧‧Metal linear structure

4‧‧‧Inorganic particles

5‧‧‧ pores

6‧‧‧Material

7‧‧‧Undercoat

8‧‧‧Electrical area

9‧‧‧ Non-conducting area

10‧‧‧Inner primer

11‧‧‧ Conductive surfaces observed from a direction perpendicular to the layer

12‧‧‧Single fibrous electrical conductor

13‧‧‧A collection of fibrous conductors

14‧‧‧Nami line

15‧‧‧ Needle-shaped electrical conductor

16‧‧‧Contacts formed by the overlap of fibrous conductors

17‧‧‧Contacts formed by the overlap of the nanowires

18‧‧‧Contacts formed by the overlap of needle-like conductors

19‧‧‧Electrical laminate

20‧‧‧Substrate of conductive laminate

21‧‧‧ Conductive layer of conductive laminate

22‧‧‧Connection layer for laminated conductive laminates

23‧‧‧Material on the side of the screen

24‧‧‧hard coating

25‧‧‧Easy layer

Fig. 1 is a schematic cross-sectional view showing a conductive laminate of an undercoat layer containing inorganic particles of the present invention.

Fig. 2 is a schematic cross-sectional view showing a conductive laminate of a conductive layer of the present invention comprising inorganic particles.

Fig. 3 is a schematic cross-sectional view showing the inner surface hard coat layer of the present invention comprising a conductive laminate of inorganic particles.

Fig. 4 is a schematic cross-sectional view showing a conductive laminate of an inorganic particle in the easy-adhesion layer of the present invention.

Figure 5 is a cross-sectional schematic view of a patterned electrically conductive laminate of the undercoat layer of the present invention comprising pores.

Figure 6 is a cross-sectional schematic view of a patterned conductive laminate of the present invention in which the patterned conductive layer comprises voids.

Figure 7 is a cross-sectional schematic view of the patterned electrically conductive laminate of the inner surface hard coat layer of the present invention comprising pores.

Figure 8 is a cross-sectional schematic view of the patterned electrically conductive laminate of the present invention having an easy-to-adhere layer comprising voids.

Fig. 9 is an example of a metal-based linear structure having a network structure.

Fig. 10 is a touch panel in which the electrically conductive laminated body of the present invention is mounted.

[Electrically conductive laminate]

The conductive laminate system substrate of the present invention has a conductive layer on at least one side thereof. That is, only one side of the substrate has a conductive layer, or it may have a conductive layer on both sides of the substrate. The conductive layer is composed of a conductive component having a network structure including a metal-based linear structure in a matrix containing a polymer having a crosslinked structure. When the conductive component having the network structure including the metal-based linear structure has a random alignment, since good optical characteristics can be obtained in addition to conductivity and durability, the display body of the conductive laminate of the present invention is used. The display becomes clear and good. The conductive laminate can also impart various functional layers such as a hard coat layer and an undercoat layer as needed. The hard coat layer can be provided on the outermost layer on the side where the conductive layer of the conductive laminate is formed, or the outermost layer on the opposite side sandwiching the substrate. The hard coat layer is mainly provided for the purpose of improving surface strength, antifouling property, fingerprint resistance, etc., and it is also possible to form fine unevenness on the surface to impart antiglare property. As the hard coat layer, a thermosetting type or an ultraviolet curable type acrylic resin can be suitably used from the viewpoint of excellent properties such as transparency and hardness during curing. The undercoat layer is provided between the substrate and the conductive layer, and is mainly provided for the purpose of improving the adhesion between the substrate and the conductive layer. From the viewpoint of adhesion to the substrate and the conductive layer, and transparency, the undercoat layer can be suitably used as a thermosetting type or an ultraviolet curing type polyester resin or propylene. Acid resin. When the conductive laminate of the present invention contains inorganic particles described later in any of the above layers, it is possible to exhibit an effect of improving the non-recognition of the pattern after patterning. Further, when the conductive layer or the undercoat layer contains inorganic particles, the effect of the non-recognition of the pattern is improved at the same time as the patterning of the conductive layer by the chemical etching method, so that the manufacturing cost is reduced due to the reduction in the number of steps. From a viewpoint, it is desirable that the conductive layer and/or the undercoat layer contain inorganic particles.

[substrate]

Specific examples of the material of the substrate of the electrically conductive laminate of the present invention include a transparent resin, glass, and the like. Examples of the resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamines, polyimine, polyphenylene sulfide, and polyarsenamide. Polyethylene, polypropylene, polystyrene, polylactic acid, polyvinyl chloride, polycarbonate, polymethyl methacrylate, etc. Methacrylic resin, alicyclic acrylic resin, cycloolefin resin, triacetyl cellulose, acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS), polyvinyl acetate, melamine resin, phenol resin Mixing and/or copolymerizing a resin containing a chlorine atom (Cl atom) such as polyvinyl chloride or polyvinylidene chloride, a fluorine atom-containing (F atom) resin, a ruthenium-oxygen resin, and a resin thereof Glass can be used with usual soda glass. Further, it is also possible to use a plurality of substrates in combination. For example, a composite substrate such as a base material of a combination resin or glass or a base material of two or more types of resin may be used. The shape of the substrate may be a film having a thickness of 250 μm or less and capable of being wound up, or a substrate having a thickness of more than 250 μm may have a region of total light transmittance described later. From the viewpoints of cost, productivity, handling, etc., the resin is thinner than 250 μm. The film is preferably a resin film of 190 μm or less, more preferably 150 μm or less, and particularly preferably 100 μm or less. When a resin film is used as the substrate, it is possible to apply a film which is not stretched, uniaxially stretched, or biaxially stretched to form a film. Among the resin films, polyethylene terephthalate (PET) or polyethylene naphthalate can be used from the viewpoints of optical properties such as moldability and transparency of the substrate, productivity, and the like. A polyester film such as a diester (PEN) or a PET film or a polypropylene film which is mixed and/or copolymerized with PEN is preferred. Further, the resin film used for the substrate may be an easy-adhesion film provided with an easy-to-attach layer on one side or both sides.

[Metal-based linear structure]

The metal-based linear structure of the present invention may, for example, be a fibrous conductor, a nanowire, a whisker or a needle-like conductor such as a nanorod. In addition, the term "fibrous" means the aspect ratio = the length of the long axis (the length of the metal-based linear structure) / the length of the short axis (the diameter of the metal-based linear structure) is more than 10. The shape is not particularly limited, and may be linear or curved, or may have a shape in which a part has a straight portion and/or a curved portion. The term "nano whisker" refers to a structure having an arc shape as exemplified in reference numeral 14 in Fig. 7, and the needle-like shape is, for example, a structure having a linear shape as exemplified in reference numeral 15 in Fig. 7. Further, the metal-based linear structure exists in addition to being formed alone, and forms an aggregate. The aggregate may be, for example, a state in which the arrangement direction of the metal-based linear structures is irregular and randomly collected, or a state in which the surfaces of the long-axis directions of the metal-based linear structures are gathered in parallel. As an example of a state in which the long-axis direction surfaces are arranged in parallel with each other, an aggregate forming a so-called bundle is known, and the metal-based linear structure may have a similar bundle structure. In the present invention The metal-based linear structure to be preferably used is a metal nanowire, and the metal composition of the metal nanowire is not particularly limited, and may be one or more of a noble metal element, a noble metal oxide, and a base metal element. It is composed of a metal, but it is preferably at least one metal belonging to a group containing a noble metal (for example, gold, platinum, silver, palladium, rhodium, iridium, ruthenium, osmium, etc.) and iron, cobalt, copper, or tin. From the viewpoint, it is preferred to contain at least silver. The nanowhisker which can be used as the metal-based linear structure of the noble metal and the noble metal oxide is described in Japanese Laid-Open Patent Publication No. 2009-505358, JP-A-2009-129607, and JP-A-2009-070660 Further, as a whisker of a metal oxide or a needle-like crystal such as a fiber, a DENTALL WK series, which is a composite oxide of potassium titanate fiber and tin and a lanthanide oxide, is commercially available (manufactured by Otsuka Chemical Co., Ltd.). ) WK200B, WK300R, WK500.

[Network Structure]

In the present invention, the network structure refers to a dispersion structure in which the number of contacts of the other metal-based linear structures is at least one more than that of the individual metal-based linear structures in the conductive layer. In this case, the contacts may be formed between any portion of the metal-based linear structure, or the end portions of the metal-based linear structures may be connected to each other, and the ends may be connected to portions other than the ends of the metal-based linear structures, and Portions other than the ends of the metal-based linear structures are connected to each other. Here, the term "connection" means that the contacts are joined, or may be simply contacted. Further, in the metal-based linear structure in the conductive layer, a part of the metal-based linear structure which does not cause formation of a network (that is, the contact is 0 and exists independently of the network) may be present.

[matrix]

The conductive layer of the present invention is preferably contained in a matrix comprising a polymer having a crosslinked structure of the metal-based linear structure.

Examples of the matrix component include organic or inorganic polymers.

The inorganic polymer may, for example, be an inorganic oxide or the like, and may be, for example, a lanthanum oxide formed by hydrolysis or polymerization by a trialkoxy decane or the like, or formed by a sputtering deposition method. Niobium oxide.

Examples of the trialkoxy decane used in this case include tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, and the like. Tetraalkoxydecanes, methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, n-propyltrimethoxydecane, n-propyltriethyl Oxydecane, isopropyltrimethoxydecane, isopropyltriethoxydecane, n-butyltrimethoxydecane, n-butyltriethoxydecane, n-pentyltrimethoxydecane, n-pentyltrifoxide Ethoxy decane, n-hexyl trimethoxy decane, n-heptyltrimethoxy decane, n-octyltrimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, cyclohexyl trimethoxy decane, Cyclohexyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, 3-chloropropyltrimethoxydecane, 3-chloropropyltriethoxydecane, 3,3,3- Trifluoropropyltrimethoxydecane, 3,3,3-trifluoropropyltriethoxydecane, 2-hydroxyethyltrimethoxydecane, 2-hydroxyethyl Triethoxysilane Silane, trimethoxy Silane 2-hydroxypropyl, 2-hydroxypropyl triethoxysilane Silane, trimethoxy Silane 3-hydroxypropyl, 3-hydroxypropyl three Ethoxy decane, 3-glycidyl propyl trimethoxy decane, 3-glycidyl propyl triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 2-( 3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-(meth)acryloxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyltriethoxydecane, Vinyl trimethoxy decane, vinyl triethoxy decane, propylene trimethoxy decane, vinyl triethoxy decane, and the like.

Examples of the organic polymer include a thermosetting resin and a photocurable resin, and examples thereof include a polyester resin, a polycarbonate resin, an acrylic resin, a methacrylic resin, an epoxy resin, and nylon. Benzoquinone Polyamide type resin, ABS resin, polyimide resin, olefin resin such as polyethylene or polypropylene, polystyrene resin, polyvinyl acetate resin, melamine resin, phenol resin, polychlorinated resin The organic polymer such as a chlorine atom (Cl atom) resin such as ethylene or polyvinylidene chloride, a fluorine atom (F atom) resin, a ruthenium oxide resin or a cellulose resin may be at the same height. Those having a crosslinked structure in the structure of a molecule and reacting them with a polymer and a crosslinking agent to form a crosslinked polymer. At least one type of the organic polymer may be selected based on the required characteristics, or two or more types may be used in combination. Among the organic polymers, a polymer containing a structure containing a compound having three or more carbon-carbon double bond groups for polymerization reaction is preferred. Such an organic polymer can be used as a raw material by including at least one component selected from the group consisting of a monomer having three or more functional groups containing a carbon-carbon double bond, an oligomer, and a polymer. It is obtained by carrying out a polymerization reaction using a carbon-carbon double bond as a reaction point.

As the functional group having a carbon-carbon double bond, a vinyl group, an isopropenyl group, an isopentenyl group, an allyl group, an acrylonitrile group, a methacryl fluorenyl group, an acryloxy group, a methacryloxy group can be exemplified. a methacrylic acid group, a acrylamide group, a methacrylamide group, an allyl group, an allylidyne group, a vinyl ether group, or a carbon-carbon double bond bonded to a group thereof The hydrogen of the carbon of the bond is substituted with a halogen atom such as fluorine or chlorine (for example, a fluorinated vinyl group, a difluorovinylidene group, a vinyl chloride group, a dichlorovinylidene group, or the like). In addition to these, a substituent (for example, a styryl group or the like) or a butadienyl group (for example, CH) containing a carbon having an aromatic ring such as a phenyl group or a naphthyl group bonded to a carbon-carbon double bond may be mentioned. ₂ = C(R1)-C(R2)=CH-, CH ₂ =C(R1)-C(=CH ₂ )-(R1, R2 is H or CH ₃ )) having a conjugated polyene structure Wait. One or two or more kinds may be used in combination depending on the characteristics and productivity required.

As a compound having three or more carbon-carbon double bonds imparting a polymerization reaction, neopentyl alcohol triacrylate, neopentyl alcohol trimethacrylate, neopentyl alcohol tetraacrylate, and neopentyl alcohol can be exemplified. Methacrylate, pentaerythritol ethoxy triacrylate, pentaerythritol ethoxy trimethacrylate, pentaerythritol ethoxy tetraacrylate, neopentyl alcohol ethoxytetramethyl Acrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate Ester, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate , trimethylolpropane ethoxy triacrylate, trimethylolpropane ethoxy trimethacrylate, di-trishydroxy Propane triacrylate, di-trimethylolpropane trimethacrylate, di-trimethylolpropane tetraacrylate, di-trimethylolpropane tetramethacrylate, glycerol propoxy triacrylate a compound having a cyclic skeleton in an molecule such as an ester, glycerol propoxytrimethacrylate, or a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring or the like (for example, triacrylate, three) a methacrylate, tetraacrylate, tetramethacrylate, pentaacrylate, pentamethyl acrylate, hexaacrylate, hexamethacrylate, etc., or a compound that partially modifies one of their compounds (eg Modified 2-hydroxypropionic acid modified neopentyl alcohol triacrylate, 2-hydroxypropionic acid modified pentaerythritol trimethacrylate, 2-hydroxypropionic acid modified with 2-hydroxypropionic acid Pentaerythritol tetraacrylate, 2-hydroxypropionic acid modified neopentaerythritol tetramethacrylate, oxirane triacrylate, helium oxide trimethacrylate, helium oxygen introduced into the oxoxane skeleton Alkyl tetraacrylate, decane tetramethacrylate, decane pentoxide, decyl pentoxide a olefinic acid ester, a decyl hexaacrylate, a decyl hexamethacrylate, or the like, or a compound having a skeleton other than a vinyl group and/or a vinylidene group in the skeleton (for example, having a urethane skeleton) Urethane triacrylate, urethane trimethacrylate, urethane tetraacrylate, urethane tetramethacrylate, urethane pentaacrylate, amine Carbamate pentamethacrylate, urethane hexaacrylate, urethane hexamethacrylate, polyether triacrylate with ether backbone, polyether trimethacrylate, polyether Tetraacrylate, polyether tetramethacrylate, polyether pentaacrylate, polyether pentamethacrylate, polyether hexaacrylate, polyether hexamethacrylate, epoxy having a skeleton derived from an epoxy group Triacrylate, epoxy III Methacrylate, epoxy tetraacrylate, epoxy tetramethacrylate, epoxy pentaacrylate, epoxy penta methacrylate, epoxy hexaacrylate, epoxy hexamethyl Acrylate, polyester triacrylate with ester backbone, polyester trimethacrylate, polyester tetraacrylate, polyester tetramethacrylate, polyester pentaacrylate, polyester penta methacrylate, poly Ester hexaacrylate, polyester hexamethacrylate, etc.). In consideration of the use, the required properties, the productivity, and the like, it is possible to use a monomer which is polymerized by a monomer or a mixture of two or more monomers, and a copolymer of two or more kinds of dimers or more. The composition formed by the polymer is not particularly limited. Among these compounds, it is more preferable to use four or more carbon-carbon double bond groups which impart a polymerization reaction, that is, a compound having four or more functions. The tetrafunctional or higher compound can be exemplified by the above-mentioned tetrafunctional tetraacrylate, tetramethacrylate, 5-functional pentaacrylate, pentamethyl acrylate, 6-functional hexaacrylate, hexamethacrylate, etc. It can also be 7 or more.

As a specific commercial product, these compounds can be exemplified by the light acrylate series, the light ester series, the epoxy ester series, the urethane acrylate AH series, and the urethane acrylate manufactured by Kyoei Chemical Co., Ltd. AT series (Urethane Acrylate AT series), Urethane Acrylate UA series, Daicel. EBECRYL series, PETIA, TMPTA, TMPEOTA, OTA 480, DPHA, PETA-K, "Full Cure series" by Synthetic Chemical Co., Ltd., and "LIODURAS" (registered trademark) by Toyo Ink Manufacturing Co., Ltd. Series, China Seed Co., Ltd., Frozen Seed series, MATSUI EXP series made by CHEMICAL Co., Ltd., Daicel. EBECRYL1360 manufactured by Cytec Co., Ltd., X-12-2456 series manufactured by Shin-Etsu Chemical Co., Ltd., etc.

[Inorganic Particles]

The electroconductive laminate system of the present invention preferably contains inorganic particles in any of its layers. The effect of changing optical characteristics is exhibited by treating the inorganic particles in the dissolution layer with a drug to generate pores.

In the present invention, the dissolved inorganic compound can be treated by using various carbonates and an acid such as zinc oxide, tin oxide, ITO or the like. Among them, from the viewpoints of easy reaction with an acid, stability to water or an alkaline solution, an organic solvent, and formation of pores by easily generating carbon dioxide upon reaction with an acid, it is preferred to use a carbonate, and it is particularly preferable to use it. Obtain easy and inexpensive calcium carbonate. The size of the inorganic particles is preferably such that the thickness of the layer containing the inorganic particles is less than 500 nm, and the average particle diameter is preferably 300 nm in order to suppress the light transmittance of the conductive laminated body from being lowered and the haze value is increased. the following. Here, the average particle diameter a of the inorganic particles is defined as a mode obtained from a distribution curve based on the number of long diameters. Also, the long diameter is the longest diameter that each of the individual inorganic particles can be recognized on the image photographed by the microscope. As a method for taking such data, an image including a cross section of the inorganic particle layer can be observed using, for example, a field emission type scanning electron microscope (SEM) (JSM-6700-F, manufactured by JEOL Ltd.). In addition, the average particle diameter of the inorganic particles of the present invention means the primary particle diameter of the inorganic particles in the case of monodispersion, and the aggregate particle size in the case of agglomerates in which a plurality of primary particles are aggregated. When the particles are in a state of agglutination, the agglutination is performed by microscopy The longest diameter that can be recognized on the image is regarded as the long diameter of the particle, and the average particle diameter a is calculated by the aforementioned method.

[pore]

The patterned conductive layer system of the present invention comprises pores in any layer of the non-conductive region. The pores exhibit a reduction in the value of the transmitted haze value and a decrease in the effect of diffusing the reflected light in the non-conductive region. The non-conductive region is caused by a decrease in the light-transmitting haze value and the diffused reflection light due to the fact that the metal-based linear structure is smaller than the conductive region, and the present invention can obtain the lift pattern by reducing the difference in optical characteristics as described above. Non-identifiable patterned conductive layer body.

The pore size of the present invention is preferably from an average pore diameter of 500 nm or less in order to reduce the thickness of the layer containing the pores, and the light transmittance of the non-conductive region of the patterned conductive laminate is lowered, and the light transmittance is increased. And efficiently obtaining diffuse reflected light, preferably having an average pore diameter of 300 nm or less. The method of measuring the average pore diameter is the same as the average particle diameter of the inorganic particles described in the above [Inorganic Particles]. At this time, the pores having a major axis of 10 nm or more which can be confirmed by observation of the image by SEM are the pores of the present invention.

Next, a method of generating pores will be described. The pores of the present invention are produced by dissolving or decomposing the aforementioned inorganic particles. Specifically, a method in which an acid or an alkaline solution is permeated into a layer containing inorganic particles, a chemical reaction dissolves the inorganic particles to form pores, or an inorganic particle is applied by external application of energy such as heat or laser. A method of decomposing to form pores. Among these methods, a method of dissolving inorganic particles to form pores by a chemical reaction is applied from the viewpoint of being able to correspond to a finely patterned conductive layer and performing other steps simultaneously with good productivity.

[layer containing inorganic particles]

The inorganic particle-containing layer of the present invention can be disposed at any position in the electrically conductive laminate. For example, it can be disposed between the substrate and the conductive layer as an undercoat layer, and can also be disposed on the reverse side of the conductive layer as a hard coat layer.

Further, it is also possible to form inorganic layer-containing layers by dispersing inorganic particles in a matrix or in an easy-adhesion layer of a substrate.

Among them, in the case of using the chemical etching method, the effect of the non-recognition of the pattern is exhibited at the same time as the patterning of the conductive layer, and the layer containing the inorganic particles is desired from the viewpoint of reducing the manufacturing cost due to the reduction in the number of steps. On the side of the conductive layer. Further, as described in the item [Inorganic Particles], in order to obtain the effect of the present invention, the average particle diameter of the inorganic particles is preferably a region, and the layer containing the inorganic particles is preferably a layer thickness sufficient to coat the inorganic particles. Specifically, a layer thickness of 200 nm or more is desired, and when the layer thickness is less than 200 nm, irregularities due to inorganic particles that cannot be coated are generated, and transparency is lowered. Further, since the pores are not generated in the layer when the inorganic particles are dissolved, the optical characteristics of the effect of the present invention cannot be obtained. In addition, the upper limit of the layer thickness is preferably 1 μm or less from the viewpoint of flexibility, handleability, and the like of the conductive laminate. From the viewpoint of the layer thickness, the layer containing the inorganic particles is preferably formed into an easy-adhesion layer of the undercoat layer or the substrate which does not affect the handleability and the contact resistance value.

As the composition of the layer containing the inorganic particles, a polymer having the same crosslinked structure as that described in the above [Substrate] can be suitably used.

The inorganic particle-containing layer of the present invention can be disposed at any position of the conductive laminate, but is preferably disposed between the substrate and the conductive layer.

That is, when only one side of the substrate has a conductive layer, it is preferred to have a layer containing inorganic particles between the substrate and the conductive layer.

Further, when the double-sided substrate has a conductive layer, it may be (i) a layer containing inorganic particles formed between any conductive layer and the substrate on both sides of the substrate, or (ii) formed on the substrate double A layer containing inorganic particles is provided between any one of the conductive layers and the substrate.

The method of forming the layer containing the inorganic particles is a method in which the inorganic particles are dispersed and applied to the substrate in a composition solution of the layer containing the inorganic particles as appropriate. Examples of the coating method include casting, spin coating, dip coating, bar coating, spray coating, blade coating, slit extrusion coating, gravure coating, reverse coating, screen printing, die coating, printing transfer, inkjet, and the like. A wet coating method or the like, in which a coating method using slit extrusion coating and micro-gravure is used, in particular, because it can be uniformly and productively coated by a roll to roll. good. Further, when the base film is formed into a film, the easy-adhesion layer solution in which the inorganic particles are dispersed is applied to the unstretched film, and an easily-adhesive layer containing inorganic particles can be formed on the stretched base film.

[patterned conductive laminate]

The patterned conductive laminate system substrate of the present invention has a patterned conductive layer on at least one side.

The patterned conductive layer has a conductive region and a non-conductive region on its inner surface. The conductive region contains a metal system having a network structure in the matrix Linear structure. The metal-based linear structure having a network structure lowers the resistance value by forming a function as a so-called conductive component, and thus exhibits conductivity required as a conductive region. The non-conductive region does not exhibit a conductivity because it does not have a metal-based linear structure or has a state in which the amount is less than that of the conductive region and does not have a network structure.

Next, a method of manufacturing the patterned conductive layer will be described. The method for manufacturing a patterned conductive layer includes a method of forming a conductive layer on one side of a substrate, removing or reducing a portion of the metal-based linear structure to form a non-conductive region, and performing screen printing and indirect gravure printing. (Offset gravure printing), a method of inkjet or the like directly forms a pattern of a conductive region. The present invention can be applied to a method in which a conductive layer is formed in the former to form a non-conductive region. As a method of integrally forming a conductive layer, a method of dispersing and coating a metal-based linear structure in the above-mentioned matrix, or a method of applying a dispersion of a metal-based linear structure, drying, coating and impregnating a matrix solution, and curing can be mentioned. Wait. Examples of the method for applying the dispersion of the metal-based linear structure and the substrate solution include casting, spin coating, dip coating, bar coating, spray coating, blade coating, slit extrusion coating, gravure coating, reverse coating, and netting. A usual method such as a wet coating method such as plate printing, mold coating, printing transfer, or inkjet. Among the coating methods, the wet coating method of microgravure printing in which the dispersion liquid can be uniformly applied to the respective substrates and the substrate is not easily damaged by the above-described respective methods, or the conductive layer can be formed uniformly and productively. It is better.

A method of forming a non-conductive region will be described later. The formation of the non-conductive region, that is, the removal or reduction of the metal-based linear structure, may be a metal-based linear structure in the matrix using an etching solution or an etching paste. A chemical etching method for disconnection and removal, and a method of disconnecting or disappearing a metal-based linear structure by laser ablation. In the present invention, the inorganic particles can be dissolved while etching the metal-based linear structure, and the chemical etching method can be suitably used because the step of generating pores in the patterned and non-conductive layers can be performed in the same step.

In the present invention, the conductive laminated layer is preferably a transparent conductive laminated body having a total light transmittance of 80% or more according to JIS K7361-1 (1997) when incident on the side of the conductive layer. The touch panel in which the conductive laminate of the present invention is assembled exhibits excellent transparency, and can clearly recognize the display of the display provided on the lower layer of the touch panel using the transparent conductive laminate. The transparency of the present invention means that the total light transmittance according to JIS K7361-1 (1997) when the light is incident from the side of the conductive layer is 80% or more, preferably 85% or more, preferably 90%. the above.

Further, in the present invention, a hard coat which imparts abrasion resistance, high surface hardness, solvent resistance, stain resistance, and the like may be applied to the reverse side of the substrate and the conductive side (the side on which the conductive layer is laminated in the present invention). Layer processing.

The conductive laminated layer of the present invention has a surface resistance value of 1 × 10 ¹ Ω/□ or more and 1 × 10 ⁴ Ω/□ or less, preferably 1 × 10 ¹ Ω/□ or more, 1.5 ×. 10 ³ Ω/□ or less. A conductive laminated body for use as a touch panel can be preferably used in this area. In other words, if the power consumption is 1 × 10 ¹ Ω/□ or more, the power consumption can be reduced, and if it is 1 × 10 ⁴ Ω/□ or less, the influence of the error in the coordinate reading of the touch panel can be reduced.

In the substrate and/or the conductive layer used in the present invention, various additives can be added in a region which does not impair the effects of the present invention. As the additive, for example, organic fine particles, a crosslinking agent, a flame retardant, and a hindrance can be used. Combustion aids, heat stabilizers, antioxidant stabilizers, leveling agents, slip activators, antistatic agents, UV absorbers, light stabilizers, nucleating agents, dyes, fillers, dispersants and coupling agents.

Further, the patterned conductor layer of the present invention can be used by laminating two or more layers. When two or more layers are laminated, it is possible to laminate by bonding layers. An adhesive or an adhesive can be used as the bonding layer, and an adhesive can be suitably used from the viewpoint of handleability and flexibility. In the present invention, an acrylic pressure-sensitive adhesive, a siloxane-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive or the like can be used, and an acrylic pressure-sensitive adhesive can be suitably used in particular from the viewpoint of adhesive properties or easy adjustment of color tone.

The conductive laminated body and/or the patterned conductive laminated body of the present invention can be preferably used for a display body, and particularly preferably used for a touch panel and an electronic paper. 8 is a cross-sectional schematic view showing an example of a touch panel. The touch panel is a single or a plurality of sheets, and a conductive laminated body of the present invention (for example, FIG. 1 ) in which a conductive layer having a network structure of a metal-based linear structure is laminated, and a resistive film can be used. As an example, a touch panel and a capacitive touch panel are used. The conductive layer of the electrically conductive laminated body of the present invention comprises (optionally or plurally) a metal-based linear structure represented by the symbols 12, 13, 14, 15 as shown in Fig. 7, formed of (optional or plural) Symbols 16, 17, and 18 indicate the network structure of the contacts. The touch panel in which the conductive laminated body of the present invention is mounted is bonded to the bonding layer 22 such as an adhesive or an adhesive to laminate the conductive laminated body 19, and the screen side of the touch panel is further provided. The substrate is a hard coat layer 24 laminated on the substrate side substrate of the touch panel. Such a touch panel is mounted, for example, with a lead wire, a driving unit, and the like, and is assembled in front of a liquid crystal display.

[layer of pores present]

The layer in which the pores of the present invention are present can be disposed at any position in the patterned conductive laminate, but is preferably disposed between the substrate and the patterned conductive layer.

That is, when only one side of the substrate has a patterned conductive layer, it is preferred that a layer having pores be present between the substrate and the patterned conductive layer.

In addition, when the patterned double-sided substrate has a patterned conductive layer, it may be (i) a layer having pores formed between any patterned conductive layer formed on both sides of the substrate and the substrate, or (ii) formed on A layer having voids between any of the patterned conductive layers and the substrate in the patterned conductive layer on both sides of the substrate.

Further, the pores of the present invention as described in [Pore] are produced by dissolving or decomposing inorganic particles. Therefore, a layer in which pores are formed is formed by impregnating an acid or an alkaline solution with an acid or an alkaline solution while applying energy from the outside by heating or laser. Since the treatment for forming the layer having the pores as described above and the process of forming the non-conductive region of the conductive laminate are simultaneously performed, the number of steps is reduced to improve productivity, so that the layer of the void is formed to be formed in the same manner as the patterned conductive layer. The face is better. Further, when the layer in which the pores are formed is formed on the more surface side than the patterned conductive layer, moisture or gas in the atmosphere easily permeates the layer, and the durability of the patterned conductive layer is also lowered. Therefore, it is preferred that a layer of pores be formed between the substrate and the patterned conductive layer.

The layer in which the pores are present is preferably only a layer thickness sufficient to coat the pores. Specifically, it is desirable that the layer thickness is 200 nm or more, and when the layer thickness is less than 200 nm, pores are not formed in the layer, and the light of the effect of the present invention cannot be obtained. Learning characteristics change. In addition, the upper limit of the layer thickness is preferably 1 μm or less from the viewpoint of flexibility, handleability, and the like of the patterned conductive laminate.

As the composition of the layer in which the pores are present, a polymer having the same crosslinked structure as that described in the above [Matrix] can be suitably used.

[Examples]

Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited by the following examples.

[evaluation method]

First, the evaluation methods of the respective examples and comparative examples will be described.

(1) Form of conductive component

A probe was applied to each side of the sample using an insulated electric meter (manufactured by Sanwa Electric Co., Ltd., DG6), and the conductive surface of the sample was identified by energization.

Next, a scanning transmission electron microscope (Hitachi Hi-Tech Co., Ltd., Hitachi Scanning Transmission Electron Microscope HD-2700) or an electric field emission type scanning electron microscope (JSM-6700-F, manufactured by JEOL Ltd.) was used, and the acceleration voltage was 3.0. kV, the observation magnification is appropriately adjusted in comparison with the image, and the surfaces of the conductive region (A) and the non-conductive region (B) of the sample are observed at various magnifications.

When it is difficult to observe by the above method, a color 3D laser microscope (VK-9700/9710, manufactured by KEYENCE Co., Ltd.), an observation application (VK-H1V1 manufactured by KEYENCE Co., Ltd.), and a shape analysis application (VK manufactured by KEYENCE Co., Ltd.) are used. -H1A1), with the attached standard lens 10X (Nikon shares limited CF IC EPI Plan 10X), 20X (CF IC EPI Plan 20X manufactured by Nikon Co., Ltd.), 50X (CF IC EPI Plan Apo 50X manufactured by Nikon Co., Ltd.), 150X (CF IC EPI Plan Apo manufactured by Nikon Co., Ltd.) 150X) The same position on the conductive side was observed on the surface at each magnification, and image analysis was performed from the image data.

(2) Identification of conductive components and inorganic particles

The conductive layer was peeled off from the sample and dissolved in a dissolved solvent. If necessary, it is suitable for the separation of each individual substance by a usual chromatography method represented by ruthenium column chromatography, gel permeation chromatography, liquid high-speed chromatography, etc., and is provided in the following qualitative analysis.

Then, the conductive component is appropriately concentrated and diluted to prepare a sample. Next, the following evaluation methods were used to identify the components contained in the sample.

The analysis method is performed by combining the following analysis methods, so that it can be preferentially applied by being able to perform measurement by a small combination.

Nuclear magnetic resonance spectroscopy ( ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR, ¹⁹ F-NMR), two-dimensional nuclear magnetic resonance spectroscopy (2D-NMR), infrared spectroscopy (IR), Raman spectroscopy , mass spectrometry (GC-MS), thermal decomposition gas chromatography-mass spectrometry (thermal decomposition GC-MS), matrix-assisted laser desorption free mass spectrometry (MALDI-MS), Time-of-flight mass spectrometry (TOF-MS), time-of-flight matrix-assisted laser desorption mass spectrometry (MALDI-TOF-MS), dynamic secondary ion mass spectrometry (Dynamic-SIMS), time-of-flight secondary ion mass spectrometry Method (TOF-SIMS), other static secondary ion mass spectrometry (Static-SIMS), etc., X-ray diffraction (XRD), neutron diffraction (ND), low energy electron diffraction (LEED), High-speed reflection electron diffraction (RHEED), atomic absorption spectrometry (AAS), ultraviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), X-ray fluorescence analysis (XRF), inductively coupled plasma atomic emission spectrometry (ICP-AES), electron probe microanalysis (EPMA), particle induced X-ray emission (PIXE), low energy ion scattering spectroscopy (RBS or LEIS), medium Energy ion Spectroscopy (MEIS), high energy scattering spectroscopy (ISS or HEIS), gel permeation chromatography (GPC), transmission electron microscopy-energy dispersive X-ray analysis (TEM-EDX), scanning electron microscopy-energy dispersion X-ray analysis (SEM-EDX), other elemental analysis of gas chromatography (GC).

(3) Surface resistance value R ₀

The surface resistance value of the conductive layer side of the central portion of the conductive laminated body of the sample of 100 mm × 50 mm was measured by an eddy current method using a non-contact resistivity meter (NC-10 manufactured by Napson Co., Ltd.). The average value was calculated for the three samples, and this was the surface resistance value R ₀ [Ω/□]. When the surface resistance value is not obtained beyond the detection limit, it is measured by the following method.

A high-resistivity meter (Hiresta-UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation) was used, and a ring-shaped probe (URS probe MCP-HTP14 manufactured by Mitsubishi Chemical Corporation) was connected to measure a sample of 100 mm × 100 mm in a double loop manner. Central part. The average value was calculated for the three samples, and this was the surface resistance value R ₀ [Ω/□].

(4) Full light transmittance, haze

On the conductive layer side of the sample, a hard coat (Folder Seed 423C manufactured by Nippon Paint Co., Ltd.) was bonded to the thickness of one side with a transparent adhesive (LUCIACS CS9621T manufactured by Nitto Denko Corporation). The PET film side of the 188 μm optical PET film was measured by using a haze meter (haze meter) NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) and measuring light from the side of the conductive layer according to JIS K7361-1 (1997). The total light transmittance and haze in the thickness direction of the laminate. The three samples were measured, and the average value of the three samples was calculated, and this was the total light transmittance and the haze of each degree. For this measurement, the value is rounded to the second decimal place.

(5) diffused reflected light

On the conductive layer side of the sample, a hard coat layer (Folder Seed 423C manufactured by Nippon Paint Co., Ltd.) was attached to a single-sided optical PET film having a thickness of 188 μm by a transparent adhesive (LUCIACS CS9621T manufactured by Nitto Denko Corporation). On the PET film side, the reflected light on the side of the conductive layer was measured using a spectrophotometer CM-2600d (manufactured by KONICA MINOLTA SENSING Co., Ltd.). The L* value of the L*a*b* color system in the SCE mode is used as an index of diffuse reflected light. The measurement is performed individually in both the conductive region and the non-conductive region, and the ΔL* value of the difference between the individual L* values is obtained.

(6) Non-identification evaluation of patterns

When the ΔL* value of the above-described diffused reflected light measurement was 0.7 or less, it was judged that the pattern was not distinguished. Moreover, the value of the surface-resistance value equivalent to the sample to be measured which does not include the inorganic particle and/or the void of the patterned conductive laminate of the present invention is the same as the value of ΔL* ₀ measured by the same diffuse reflected light. The ΔL* ₀ value varies depending on the amount of the metal-based linear structure, that is, the surface resistance value of the conductive laminate. For example, when the amount of the metal-based linear structure is large and the surface resistance value is low, the value of ΔL* ₀ becomes large. Here, when ΔL*-ΔL* ₀ ≦-0.3 of the same surface resistance value, it is judged that the pattern non-recognition is improved, and when ΔL*-ΔL* ₀ >-0.3, the non-recognition of the pattern is not obtained. Improvement is not good. Further, the equivalent surface resistance value means an equivalent surface resistance value in a region of a certain value of ±15 Ω/□.

(7) Determination of △L* ₀ value

None of the prepared layers contained four kinds of conductive laminates having surface resistance values of inorganic particles of 140.1 Ω/□, 150.5 Ω/□, 162.0 Ω/□, and 51.0 Ω/□. The ΔL* of the patterned electroconductive laminate obtained by patterning them is 1.93, 1.96, 2.02, and 3.27, respectively, and the individual values are ΔL* ₀ of the surface resistance value thereof. The conductive laminate and the patterned conductive laminate system at this time were obtained in the same manner as in Comparative Examples 1 and 2 to be described later.

(8) Damp heat durability test

A sample which was cut into a size of 100 mm × 50 mm was placed in a thermo-hygrostat (PR-3SP manufactured by TABAI ESPEC Co., Ltd.) operating at 60 ° C and 90% RH under a temperature and humidity condition, and the surface resistance value was taken out after 240 hours. The rate of change of the surface resistance value before and after the surface resistance value test (unit: %) was calculated by the following calculation formula. Further, the measurement of the surface resistance value was also carried out by the method described in (3) before and after the test.

(surface resistance value of sample after test/surface resistance value of sample before test) × 100 (%)...

[material] <Substrate>

A polyethylene terephthalate film ("Lumirror" (registered trademark) U48, manufactured by Toray Industries, Inc.) having a thickness of 125 μm was used.

<Metal-based linear structure>

Metal-based linear structure "silver nanowire"

Silver nanowire (short axis: 50~100nm, long axis: 20~40μm)

<matrix and undercoat>

(1) Acrylic composition A

An acrylic composition containing a compound having three or more carbon-carbon double bond groups for promoting polymerization as a propylene group (Fullure HC-6 manufactured by Soken Chemical Co., Ltd., solid content concentration: 51% by mass). The cured product has a crosslinked structure.

(2) Photopolymerization initiator A

. A photopolymerization initiator (Ciba IRGACURE (registered trademark) 907, manufactured by Chiba. Japan Co., Ltd.) was used to absorb a wavelength of 300 nm.

(3) Photopolymerization initiator B

. A photopolymerization initiator having a maximum absorption wavelength of 320 nm (Ciba IRGACURE (registered trademark) 369, manufactured by Chiba Japan Co., Ltd.).

<Easy layer composition>

(1) Coating A

An aqueous dispersion containing an acrylic resin having the following copolymerization composition dispersed in a particle form in water (that is, an emulsion coating liquid having an emulsion particle diameter of 50 nm)

. Copolymerization

(2) Coating liquid B

An aqueous dispersion of an ammonium salt type in which a polyester resin having the following copolymerization composition is dispersed in a particulate form in water

. Acid component

. Glycol component

<Inorganic Particles>

Inorganic particle A

Calcium carbonate microparticle powder which has been surface-treated with fatty acid (Calflex C manufactured by Newlime Co., Ltd., primary average particle diameter of 40 nm)

Inorganic particle B

Calcium carbonate dispersion (NK-03, manufactured by Marui Co., Ltd., solid content concentration: 20% by mass, average particle diameter: 300 nm)

Inorganic particle C

Calcium carbonate fine particle powder (VisCal P manufactured by Newlime Co., Ltd., primary average particle diameter: 150 nm) which has been surface-treated with a fatty acid.

[Example 1]

5.0 g of inorganic particles A, 95.0 g of ethyl acetate, 200.0 g of zirconia beads having an average particle diameter of 0.4 mm, and a vibrating machine SR-2DW (Taitec) After the conditions of vibration of 300 times/min were shaken for 2 hours and dispersed, the zirconia beads were removed by filtration to obtain a dispersion of inorganic particles A.

Next, 53.5 g of an acrylic composition A, 1.29 g of a photopolymerization initiator A, 1.29 g of a photopolymerization initiator B, 886.9 g of ethyl acetate, and 60.0 g of the dispersion of the above inorganic particles A were mixed and stirred to prepare a primer. Layer material. The undercoat material was applied to the substrate using a slit extrusion coater having a gasket of sus (the thickness of the gasket of 50 μm), and dried at 120 ° C for 2 minutes, and then irradiated with ultraviolet rays of 80 mJ/cm ^{2 to} be hardened. An undercoat layer having a thickness of 600 nm.

Subsequently, a silver nanowire dispersion (CleraOhm Ink-A AQ manufactured by Cambrios, USA) was prepared as an aqueous dispersion containing a metal-based linear structure. The silver nanowire dispersion was diluted to a silver nanowire concentration of 0.054% by mass to prepare a silver nanowire dispersion coating liquid. The silver nanowire dispersion coating liquid was applied onto the undercoat layer by using a slit extrusion coater having a gasket of sus material (gasket thickness: 50 μm), and dried at 120 ° C for 2 minutes to form a conductive layer. ingredient.

Next, 26.7 g of the acrylic composition A, 0.16 g of the photopolymerization initiator A, 0.16 g of the photopolymerization initiator B, and 972.0 g of ethyl acetate were mixed and stirred to prepare a matrix composition.

The prepared matrix composition was applied to the side of the laminated conductive component using a slit extrusion coater having a gasket of sus material (gasket thickness: 50 μm), and dried at 120 ° C for 2 minutes, and then irradiated at 80 mJ/cm. ^{2 The} ultraviolet rays were hardened to form a conductive layer having a thickness of the substrate portion of 120 nm to obtain a conductive laminate.

The conductive laminate is a conductive laminate in which the undercoat layer contains inorganic particles, and the inorganic particles are calcium carbonate and contained in an amount of 10% by mass based on the undercoat layer. The average particle diameter of the inorganic particles was 152 nm. Further, the surface resistivity R ₀ of the electrically conductive laminated body was 154.8 Ω/□.

Subsequently, the obtained electroconductive laminate was cut into three pieces of 50 mm × 100 mm in size to prepare a sample for non-identification confirmation as a pattern.

Next, the etching liquid mixed with a mass ratio of 36% by mass hydrochloric acid: 60% by mass of nitric acid:water of 20:3:17 was heated to 45 ° C, and only half of the sample (50 mm × 50 mm region) was immersed in the sample. Minutes for etching. Thereby, a region in which the region immersed in the etching liquid is changed into a non-conductive region, and the region other than the conductive region is a patterned conductive laminate sample is obtained. The non-conductive region of the patterned conductive laminate includes pores having an average pore diameter of 160 nm, and the pattern is not discernible, and is similar to the patterned conductive laminate without equivalent inorganic particles and/or pores. Non-identification has improved.

[Embodiment 2]

A conductive component was formed on the substrate by the same material and method as in Example 1.

Next, a dispersion of the inorganic particles A was obtained in the same manner and in the same manner as in Example 1.

Subsequently, 53.5 g of an acrylic composition A, 0.32 g of a photopolymerization initiator A, 0.32 g of a photopolymerization initiator B, 886.9 g of ethyl acetate, and 60.0 g of a dispersion of the above inorganic particles A were mixed and stirred to prepare a matrix composition. .

The prepared matrix composition was applied to the side of the laminated conductive component using a slit extrusion coater having a gasket of sus material (gasket thickness: 50 μm), and dried at 120 ° C for 2 minutes, and then irradiated at 80 mJ/cm. ² Ultraviolet rays were hardened to form a conductive layer having a thickness of 600 nm in the matrix portion, and a conductive laminate was obtained.

The conductive laminate is a conductive laminate in which a matrix contains inorganic particles, and the inorganic particles are calcium carbonate and contained in an amount of 10% by mass based on the matrix material. The average particle diameter of the inorganic particles was 145 nm. Further, the surface resistivity R ₀ of the electrically conductive laminated body was 156.0 Ω/□.

Next, a patterned conductive laminate sample was obtained in the same manner as in Example 1. The non-conductive region of the patterned conductive laminate includes pores having an average pore diameter of 164 nm, and the pattern is non-recognizable, and is compared with a patterned conductive laminate without equivalent inorganic particles and/or pores. The non-identification has improved.

[Example 3]

A dispersion of the inorganic particles A was obtained in the same manner as in Example 1.

Next, 53.5 g of an acrylic composition A, 1.29 g of a photopolymerization initiator A, 1.29 g of a photopolymerization initiator B, 886.9 g of ethyl acetate, and 60.0 g of a dispersion of the above inorganic particles A were mixed and stirred to prepare a hard coat. Layer material. The hard coat material was applied to a substrate using a slit extrusion coater having a gasket of sus (gas thickness: 50 μm), and dried at 120 ° C for 2 minutes, and then hardened by irradiation with 80 mJ/cm ^{2 of} ultraviolet rays. A hard coat layer having a thickness of 600 nm was formed.

Next, a conductive component and a matrix were formed on the reverse side of the hard coat layer formed in the same manner as in Example 1 to obtain a conductive laminate.

The conductive laminate is a conductive laminate in which a hard coat layer formed on the opposite side of the conductive layer contains inorganic particles, and the inorganic particles are calcium carbonate and are contained in an amount of 10% by mass based on the hard coat material. The average particle diameter of the inorganic particles was 149 nm. Further, the surface resistivity R ₀ of the electroconductive laminate was 167.3 Ω/□.

Next, a patterned conductive laminate sample was obtained in the same manner as in Example 1. The non-conductive region of the patterned conductive laminate comprises pores having an average pore diameter of 151 nm, and the pattern is not discernible, and the pattern is compared with the patterned conductive laminate without equivalent inorganic particles and/or pores. The non-identification has improved. Further, since the pattern of the patterned electroconductive laminate of the present embodiment includes a layer in which inorganic particles and/or pores sandwich the substrate and is located on the electroconductive laminate and the opposite surface, it is necessary to separately perform patterning processing on both sides.

[Example 4]

In addition to the undercoat material composition of 53.5 g of acrylic composition A, 1.29 g of photopolymerization initiator A, 1.29 g of photopolymerization initiator B, 801.4 g of ethyl acetate, and 150.0 g of inorganic particle A dispersion, silver coating A conductive laminate was obtained in the same manner as in Example 1 except that the condition of the nanowire dispersion was 75 μm and the wet film thickness was adjusted to 1.5 times.

The conductive laminate is a conductive laminate in which the undercoat layer contains inorganic particles, and the inorganic particles are calcium carbonate and contained in an amount of 25% by mass based on the undercoat material. The average particle diameter of the inorganic particles was 154 nm. Further, the surface resistivity R ₀ of the electrically conductive laminated body was 50.3 Ω / □.

Then, a patterned conductive laminate was obtained in the same manner as in Example 1. The non-conductive region of the patterned conductive laminate includes pores having an average pore diameter of 155 nm, and the pattern is not discernible, and is similar to the patterned conductive laminate without equivalent inorganic particles and/or pores. Non-identification has improved.

[Example 5]

In addition to the undercoat material composition of 53.5 g of acrylic composition A, 1.29 g of photopolymerization initiator A, 1.29 g of photopolymerization initiator B, 931.9 g of ethyl acetate, and 15.0 g of inorganic particles B, 1 The same method was used to obtain a conductive laminate.

The conductive laminate is a conductive laminate in which the undercoat layer contains inorganic particles, and the inorganic particles are calcium carbonate and contained in an amount of 10% by mass based on the undercoat material. The average particle diameter of the inorganic particles was 284 nm. Further, the surface resistivity R ₀ of the electroconductive laminate was 153.5 Ω/□.

Then, a patterned conductive laminate was obtained in the same manner as in Example 1. Although the non-conductive region of the patterned conductive laminate contains pores having an average pore diameter of 303 nm and the non-recognition of the pattern fails to reach a good level, the patterned surface conduction does not include inorganic particles and/or pores. The comparison of laminates has improved.

[Embodiment 6]

Except for the dispersion of the undercoat material composition of 53.5 g of the acrylic composition A, 1.29 g of the photopolymerization initiator A, 1.29 g of the photopolymerization initiator B, 829.9 g of ethyl acetate, and 120.0 g of the inorganic particles A, A conductive laminate was obtained in the same manner as in Example 1.

The conductive laminate is a conductive laminate in which the undercoat layer contains inorganic particles, and the inorganic particles are calcium carbonate and contained in an amount of 20% by mass based on the undercoat material. The average particle diameter of the inorganic particles was 154 nm. Further, the surface resistivity R ₀ of the electroconductive laminate was 57.5 Ω/□.

Then, a patterned conductive laminate was obtained in the same manner as in Example 1. Although the non-conductive region of the patterned conductive laminate contains pores having an average pore diameter of 156 nm and the pattern non-recognition fails to reach a good level, and the patterned surface conductivity does not include inorganic particles and/or pores. The comparison of laminates has improved.

[Embodiment 7]

Except for the dispersion of the undercoat material composition of 53.5 g of the acrylic composition A, 1.29 g of the photopolymerization initiator A, 1.29 g of the photopolymerization initiator B, 915.4 g of ethyl acetate, and 30.0 g of the inorganic particles A, A conductive laminate was obtained in the same manner as in Example 1.

The conductive laminate is a conductive laminate in which the undercoat layer contains inorganic particles, and the inorganic particles are calcium carbonate and contained in an amount of 5% by mass based on the undercoat material. The average particle diameter of the inorganic particles was 161 nm. Further, the surface resistivity R ₀ of the electroconductive laminate was 144.2 Ω/□.

Then, a patterned conductive laminate was obtained in the same manner as in Example 1. Although the non-conductive region of the patterned conductive laminate contains pores having an average pore diameter of 160 nm and the unrecognition of the pattern fails to reach a good level, the patterned surface conduction does not include inorganic particles and/or pores. The comparison of laminates has improved.

[Embodiment 8]

A conductive laminate was obtained in the same manner as in Example 1 except that the silver nanowire dispersion was applied under the conditions of a gasket thickness of 75 μm and a wet film thickness of 1.5.

The conductive laminate is a conductive laminate in which the undercoat layer contains inorganic particles, and the inorganic particles are calcium carbonate and contained in an amount of 10% by mass based on the undercoat material. The average particle diameter of the inorganic particles was 144 nm. Further, the surface resistivity R ₀ of the electroconductive laminate was 50.8 Ω/□.

Then, a patterned conductive laminate was obtained in the same manner as in Example 1. Although the non-conductive region of the patterned conductive laminate contains pores having an average pore diameter of 152 nm and the non-recognition of the pattern fails to reach a good level, the patterned surface conduction does not include inorganic particles and/or pores. The comparison of laminates has improved.

[Embodiment 9]

In addition to 5.0 g of inorganic particles A and 95.0 g of ethyl acetate, the dispersion was dispersed for 2 hours under the conditions of a power of 160 W by an ultrasonic cleaner US-2R (manufactured by As-1 Co., Ltd.) to obtain a dispersion of inorganic particles A. A conductive laminate was obtained in the same manner as in Example 1 except for the above.

The conductive laminate is a conductive laminate in which the undercoat layer contains inorganic particles, and the inorganic particles are calcium carbonate and contained in an amount of 10% by mass based on the undercoat material. The average particle diameter of the inorganic particles was 641 nm. Further, the surface resistivity R ₀ of the electroconductive laminate was 163.3 Ω/□.

Then, a patterned conductive laminate was obtained in the same manner as in Example 1. Although the non-conductive region of the patterned conductive laminate includes pores having an average pore diameter of 711 nm and the pattern non-recognition fails to reach a good level, the same surface resistance value does not include inorganic particles. The comparison of the patterned conductive laminates of the pores and/or pores has been improved. Further, the patterned conductive layer exhibits an increase in haze value.

[Embodiment 10]

In addition to mixing 10.0 g of inorganic particles C, 54.0 g of water, 36.0 g of isopropyl alcohol, and 200.0 g of zirconia beads having an average particle diameter of 0.4 mm, the vibration machine SR-2DW (manufactured by TIETECH Co., Ltd.) was used for 300 times of vibration. After the conditions of the reaction were shaken for 2 hours and dispersed for 2 hours, the dispersion of the inorganic particles C was obtained by removing zirconia beads by filtration.

Subsequently, the PET pellets (exclusive viscosity 0.63 dl/g) containing no externally added particles were sufficiently vacuum-dried, and then supplied to an extruder to be melted at 285 ° C, extruded from a T-shaped die into a sheet shape, and externally applied with static electricity. The electrostatic application casting method was taken up by a mirror casting drum having a surface temperature of 25 ° C to be cooled and solidified. The unstretched film was heated to 90 ° C and extended 3.4 times in the machine direction to form a uniaxially stretched film. A corona discharge treatment was performed on the single side of the film in air. Further, in the solid content ratio, the dispersion of the coating liquid A/coating liquid B/inorganic particle C=25/75/8.4, the dispersion of the coating liquid A, the coating liquid B, and the inorganic particle C of the easy-adhesion layer composition The material was applied as an easy-to-layer coating liquid to the corona discharge treated surface of the uniaxially stretched film.

Next, the uniaxially stretched film coated with the easy-to-apply coating liquid is fixed by a jig and guided to the preheating zone, dried at an ambient temperature of 75 ° C and heated to 110 ° C using a radiant heater, and dried again at 90 ° C, and then continued at 120 ° The heating zone of ° C was continuously extended 3.5 times in the width direction, followed by heat treatment in a heating zone of 220 ° C for 20 seconds to prepare a laminated film having crystal orientation as a substrate film. At this time, the thickness of the base film was 125 μm, and the thickness of the easy-adhesion layer was 350 nm.

Next, a conductive component and a matrix were laminated on the substrate in the same manner as in Example 4 to obtain a conductive laminate. The electrically conductive laminated body is a conductive laminated body in which an easy-to-adhere layer contains inorganic particles, and the inorganic particles are calcium carbonate and are contained in an amount of 7.7% by mass based on the easily-adhesive layer composition. The average particle diameter of the inorganic particles was 155 nm. Further, the surface resistivity R ₀ of the electroconductive laminate was 53.0 Ω/□.

Then, a patterned conductive laminate was obtained in the same manner as in Example 1. Although the non-conductive region of the patterned conductive laminate contains pores having an average pore diameter of 161 nm and the pattern non-recognition fails to reach a good level, and the patterned surface conductivity does not include inorganic particles and/or pores. The comparison of laminates has improved.

[Comparative Example 1]

Conduction was conducted in the same manner as in Example 1 except that the undercoat material composition was 53.5 g of the acrylic composition A, 1.29 g of the photopolymerization initiator A, 1.29 g of the photopolymerization initiator B, and 943.9 g of ethyl acetate. Laminated body.

The conductive laminate does not contain inorganic particles in any of the layers. The surface resistivity R ₀ of the electroconductive laminate was 152.7 Ω/□.

Then, a patterned conductive laminate was obtained in the same manner as in Example 1. The non-conductive region of the patterned conductive laminate has no pores in any layer, and the pattern is low in non-recognition.

[Comparative Example 2]

A conductive laminate was obtained in the same manner as in Comparative Example 1, except that the conditions for coating the silver nanowire dispersion were such that the thickness of the spacer was 75 μm and the thickness of the adjusted wet film was 1.5.

The conductive laminate does not contain inorganic particles in any of the layers. The surface resistivity R ₀ of the electroconductive laminate was 53.8 Ω/□.

Then, a patterned conductive laminate was obtained in the same manner as in Example 1. The non-conductive region of the patterned conductive laminate has no voids in any of the layers, and the pattern is low in non-recognition.

[Industry use possibility]

The conductive laminated body and the patterned electrically conductive laminated body of the present invention are suitable for use in a display body such as a touch panel, a liquid crystal display, or an electronic paper because of poor pattern recognition.

1‧‧‧Substrate

2‧‧‧ Conductive layer

3‧‧‧Metal linear structure

4‧‧‧Inorganic particles

6‧‧‧Material

7‧‧‧Undercoat

Claims (15)

A conductive laminated body comprising a conductive layered body having a conductive layer on at least one side of a substrate, wherein the conductive layer comprises a metal-based linear structure having a network structure, and further any layer of the conductive laminated body comprises inorganic particle. The conductive laminate according to claim 1, wherein the substrate and the conductive layer have a layer containing inorganic particles. A patterned conductive laminate body, which is a patterned conductive laminate body having a patterned conductive layer on at least one side of a substrate, wherein the patterned conductive layer has a conductive structure in which a metal-based linear structure having a network structure exists. The region, and the non-conductive region in which the metal-based linear structure having the network structure is not present, and the void layer is present in any layer of the laminated structure of the non-conductive region. The patterned conductive laminate according to claim 3, wherein the substrate and the patterned conductive layer have a layer having pores therebetween. The patterned conductive laminate according to claim 4, wherein the non-conductive region has more pores than the conductive region. A method for producing a patterned electrically conductive laminated body, which is a method for producing a patterned electrically conductive laminated body according to any one of claims 3, 4, and 5, which is characterized in that it is dissolved by a chemical treatment as applied The inorganic particles of the electroconductive laminate of the first or second aspect of the patent form pores. The method for producing a patterned electrically conductive laminate according to claim 6, wherein the pores are formed by dissolving the inorganic particles by treatment with a chemical, and the metal-based linear structure having a network structure is also removed to form a non-conductive region. A patterned electrically conductive laminated body obtained by the method of producing a patterned electrically conductive laminated body according to claim 6 or 7. The conductive laminate according to claim 1, wherein the metal linear structure is a silver nanowire. The conductive laminate according to claim 1, wherein the inorganic particles have an average particle diameter of 500 nm or less. The patterned electrically conductive laminate according to any one of claims 3, 4, 5, and 8, wherein the non-conductive region comprises pores having an average pore diameter of 500 nm or less. The conductive laminate according to claim 1, wherein the inorganic particles are carbonates. A display body using the conductive laminate of the first aspect of the patent application or the patterned conductive laminate according to any one of claims 3, 4, 5 and 8. A touch panel using the display body of claim 13 of the patent application. An electronic paper using the display body of claim 13 of the patent application.