TW201702739A - Photosensitive conductive film, method for forming conductive pattern, substrate having conductive pattern, and touch panel sensor - Google Patents

Abstract

A photosensitive conductive film provided with a support film and a photosensitive layer provided on the support film, the photosensitive layer containing conductive fibers, a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and an ultraviolet absorber.

Description

Photosensitive conductive film, method for forming conductive pattern, substrate with conductive pattern, and touch panel sensor

The present invention relates to a photosensitive conductive film, a method of forming a conductive pattern, a substrate with a conductive pattern, and a touch panel sensor.

LCD for large electronic devices such as personal computers and TVs, small electronic devices such as car navigation, mobile phones, and electronic dictionaries, display devices for office automation (OA) equipment, factory automation (FA) equipment, etc. Display component or touch panel sensor. Transparent electrode materials are required in these liquid crystal display elements and touch panel sensors.

Touch panels have been put into practical use in various ways. In recent years, touch panels using electrostatic capacitance have been promoted. In the capacitive touch panel, if the fingertip (conductor) is in contact with the touch input surface, electrostatic capacitance is combined between the fingertip and the conductive film to form a capacitor. The capacitive touch panel detects its coordinates by capturing changes in the charge at the contact position of the fingertip.

In particular, the projection type capacitive touch panel can perform multi-point detection of a fingertip, and therefore has good operability for performing complicated instructions. Since the operability is good, the projection type capacitive touch panel is used as an input device on the display surface in a device having a small display device such as a mobile phone or a portable music player.

Generally, in a projection type capacitive touch panel, in order to express two-dimensional coordinates of the X-axis and the Y-axis, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes form a two-layer structure. Transparent electrode materials are used in these electrodes.

Conventionally, in the transparent electrode material, indium tin oxide (ITO), indium oxide, tin oxide, or the like is used in order to exhibit high light transmittance. However, it has recently been attempted to use a material instead of the above to form a transparent electrode (transparent conductive pattern). For example, Patent Document 1 listed below proposes a method of forming a conductive pattern using a photosensitive conductive film including a photosensitive layer containing conductive fibers. If this technique is used, the conductive pattern can be directly and easily formed by a photolithography step on a plurality of substrates. [Prior Art Document] [Patent Literature]

[Patent Document 1] International Patent Publication No. 2010/021224

[Problems to be Solved by the Invention] In the photosensitive conductive film described in Patent Document 1, although a conductive pattern can be easily formed on a plurality of substrates, the inventors have found that photosensitive light containing conductive fibers is used. When the layer is subjected to exposure, development, and patterning, there is a tendency that the resolution is lowered.

An object of the present invention is to provide a photosensitive conductive film and a method for forming a conductive pattern which can form a conductive pattern of conductive fibers with sufficient resolution, and a conductive patterned substrate having a conductive pattern having excellent resolution. And the touch panel.

[Means for Solving the Problem] In order to solve the above problems, the present inventors have found that the ultraviolet absorbing agent can be blended in a photosensitive layer containing conductive fibers, whereby the resolution can be improved, and the present invention can be completed.

The present invention provides a photosensitive conductive film comprising a support film and a photosensitive layer provided on the support film, and the photosensitive layer contains a conductive fiber, a binder polymer, a photopolymerizable compound, and a photopolymerization initiation Agent and UV absorber.

According to the photosensitive conductive film of the present invention, a conductive pattern containing conductive fibers can be formed with sufficient resolution. It is presumed that the reason is that, by having the composition in which the photosensitive layer contains the ultraviolet absorber, when the patterning is performed, the scattered light generated by the conductive fibers can be absorbed, and the influence by halation can be reduced. .

The ultraviolet absorber can also have a maximum absorption wavelength in a wavelength range of 250 nm or more and 400 nm or less. Such an ultraviolet absorber can effectively absorb scattered light caused by the conductive fibers, and can suppress the decrease in resolution more highly.

The minimum value of the visible light transmittance in the photosensitive conductive film at 400 nm to 700 nm may be 85% or more. When the minimum value of the visible light transmittance is within the above range, a conductive pattern excellent in coloring and excellent in transparency can be provided.

The ultraviolet absorber may also have a thermally polymerizable group or a photopolymerizable group. In the case of using such an ultraviolet absorber, the permeation of the ultraviolet absorber from the photosensitive layer or the cured product thereof can be further suppressed.

The ultraviolet absorber may also be a polymer type ultraviolet absorber. In the case of using such an ultraviolet absorber, the permeation of the ultraviolet absorber from the photosensitive layer or the cured product thereof can be further suppressed.

The conductive fibers may also be silver fibers. By using silver fibers, it is possible to provide a photosensitive conductive film having high visible light transmittance in a wavelength range of 400 nm or more and 700 nm or less and having high conductivity.

Further, the present invention provides a method of forming a conductive pattern, comprising: a step of transferring a photosensitive layer of the photosensitive conductive film of the present invention onto a substrate; and an exposing step of transferring the substrate onto the substrate a photosensitive layer that irradiates the actinic rays in a pattern; and a developing step of forming a conductive pattern by removing unexposed portions of the photosensitive layer.

According to the method for forming a conductive pattern of the present invention, even in the case of a photosensitive layer containing conductive fibers, a conductive pattern can be formed with sufficient resolution. According to the method of forming the conductive pattern, the conductive pattern can be easily formed on the substrate.

Further, the present invention provides a substrate with a conductive pattern comprising a substrate and a conductive pattern formed on the substrate by a method of forming a conductive pattern of the present invention.

Since the conductive pattern-containing substrate of the present invention has a conductive pattern formed by the formation method of the conductive pattern, it can have a conductive pattern excellent in resolution, that is, a finer conductive pattern and a thinner space portion (photosensitive) Layer removal section).

In addition, the present invention provides a touch panel sensor comprising the substrate with a conductive pattern of the present invention.

Since the touch panel sensor of the present invention includes the substrate with the conductive pattern described above, the pattern visibility of the conductive pattern can be reduced, and the visibility can be improved (the pattern is not easily seen).

[Effect of the Invention] According to the present invention, it is possible to provide a method for forming a photosensitive conductive film and a conductive pattern which can form a conductive pattern of conductive fibers with sufficient resolution, and a conductive pattern having a conductive pattern having excellent resolution. Substrate and touch panel.

Hereinafter, preferred embodiments of the present invention will be described in detail. The term "(meth)acrylate" in the present specification means "acrylate" or "methacrylate". Similarly, "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid", and "(meth)acrylic acid group" means "acrylic acid" or "methacryl fluorenyl". In addition, the numerical range represented by "~" indicates the range including the numerical values described before and after "~" as the minimum value and the maximum value. The term "A or B" means that any one of A and B may be included, and both may be included. In addition, unless otherwise indicated, the exemplified materials may be used singly or in combination of two or more.

<Photosensitive Conductive Film> The photosensitive conductive film of the present embodiment includes a support film and a photosensitive layer provided on the support film, and the photosensitive layer contains a conductive fiber, a binder polymer, a photopolymerizable compound, Photopolymerization initiator and UV absorber. An embodiment of the photosensitive conductive film is shown in Fig. 1 . The photosensitive conductive film 10 includes a support film 1, a photosensitive layer 4, and a protective film 5, and the photosensitive layer 4 includes a conductive film 2 and a photosensitive resin layer 3. The conductive film 2 contains conductive fibers. Further, the photosensitive conductive film is used to transfer a photosensitive layer onto a substrate to form a photosensitive layer on the substrate, and thus may be referred to as a transfer-type photosensitive conductive film.

In FIG. 1, the boundary between the conductive film 2 of the photosensitive conductive film 10 and the photosensitive resin layer 3 provided on the conductive film 2 is clearly described, but the boundary between the conductive film 2 and the photosensitive resin layer 3 may not necessarily be clear. The conductive film may have a conductivity in the surface direction of the photosensitive layer, or may be a form in which a photosensitive resin layer is mixed in the conductive film. For example, a composition constituting the photosensitive resin layer may be impregnated into the conductive film, or a composition constituting the photosensitive resin layer may be present on the surface of the conductive film.

Hereinafter, the support film 1 including the photosensitive conductive film 10, the photosensitive layer 4 (the conductive film 2 and the photosensitive resin layer 3), and the protective film 5 will be described in detail.

The support film 1 is a polymer film having heat resistance and solvent resistance. Examples of such a polymer film include a polyethylene terephthalate film, a polyethylene film, a polypropylene film, and a polycarbonate film. Among these polymer films, a polyethylene terephthalate film is preferred from the viewpoint of transparency and heat resistance. Further, the polymer films may be subjected to a surface treatment so as to be easily peeled off from the photosensitive layer 4, preferably a material which is easily peeled off from the photosensitive layer 4.

The thickness of the support film 1 is preferably from 5 μm to 300 μm, more preferably from 10 μm to 200 μm, still more preferably from 15 μm to 100 μm, particularly preferably from 30 μm to 70 μm. The step of applying a conductive dispersion liquid to form the conductive film 2 or applying a photosensitive resin composition for forming the photosensitive resin layer 3, or peeling off the support film before developing the exposed photosensitive resin layer 3 In the step, from the viewpoint of preventing the mechanical strength from decreasing and the support film from being broken, it is preferably 5 μm or more, more preferably 10 μm or more, particularly preferably 15 μm or more, and particularly preferably 30 μm or more. In addition, from the viewpoint of further improving the resolution of the pattern when the actinic resin layer is irradiated with the actinic ray, the preferred pattern is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 100. Below μm, it is particularly preferably 70 μm or less.

The haze value of the support film 1 is preferably from 0.01% to 5.0%, more preferably from 0.01% to 3.0%, even more preferably from 0.01% to 2.0%, particularly preferably from the viewpoint of good sensitivity and resolution. 0.01% to 1.0%. Further, the haze value can be measured in accordance with JIS K 7375 (developed in 2008). In addition, it can also be measured by a commercially available turbidity meter or the like using NDH-1001DP (manufactured by Nippon Denshoku Industries Co., Ltd., trade name).

Examples of the conductive fiber include metal fibers such as gold, silver, copper, and platinum, and carbon fibers such as carbon nanotubes. The method for preparing the conductive fiber is simple, and the shape of the conductive fiber is easily controlled, and the visible light transmittance is high in the wavelength range of 400 nm to 700 nm, and the conductive fiber is superior in terms of high conductivity. Good for silver fiber, better for silver nanowire. Here, the nanowire includes, for example, a small difference in size between two dimensions (X, Y) (specifically, a difference in size is 5 times or less) and X and Y are both 300 nm or less, and the remainder The dimension of one dimension (Z) is more than 10 times the shape of X and Y.

Fig. 2 is a partially cutaway perspective view showing an embodiment of a photosensitive conductive film. The conductive film 2 is preferably a mesh structure in which conductive fibers are in contact with each other like the photosensitive conductive film 12 shown in FIG. 2 . The conductive film 2 having such a mesh structure can be formed on the surface of the photosensitive resin layer 3 on the support film 1 side, but if the surface of the photosensitive layer 4 exposed when the support film 1 is peeled off, conductivity is obtained in the surface direction thereof. In addition, a part of the photosensitive resin layer 3 may be formed in the conductive film 2, or may be formed in the surface layer of the photosensitive resin layer 3 on the side of the support film 1 including the conductive film 2.

The conductive fiber containing a silver fiber or a silver nanowire can be prepared, for example, by a method of reducing silver ions with a reducing agent such as NaBH ₄ or a polyol method.

The fiber diameter of the conductive fiber is preferably from 1 nm to 100 nm, more preferably from 2 nm to 50 nm, and particularly preferably from 3 nm to 30 nm. Further, the fiber length of the conductive fiber is preferably from 1 μm to 100 μm, more preferably from 2 μm to 50 μm, still more preferably from 3 μm to 10 μm. The fiber diameter and fiber length can be measured by a scanning electron microscope.

In the conductive film 2, an organic conductor may be used in combination with the conductive fibers. The organic conductor can be used without particular limitation, and from the viewpoint of high transparency and conductivity, an organic conductor such as a polymer of a thiophene derivative or an aniline derivative is preferably used. Specifically, polyethylene dioxythiophene, polyhexylthiophene, polyaniline, polyvinylpyrrolidone or the like can be used.

The thickness of the conductive film 2 also differs depending on the use of the conductive pattern formed by using the photosensitive conductive film of the present invention or the required conductivity, and is preferably 1 μm or less, more preferably 1 nm to 0.5 μm, and particularly preferably 5 nm to 0.1 μm. When the thickness of the conductive film 2 is 1 μm or less, the light transmittance in the wavelength range of 400 nm to 700 nm is high, and the pattern formation property is also excellent, and it is particularly suitable for producing a transparent electrode. The thickness of the conductive film 2 refers to a value measured by a scanning electron microscope.

The conductive film 2 can be applied to the support film 1 by, for example, a conductive dispersion liquid to which the conductive fiber or the organic conductor is added and water or an organic solvent, a dispersion stabilizer such as a surfactant, or the like is added. Thereafter, it is formed by drying. After drying, the conductive film 2 formed on the support film 1 may be laminated as needed.

The coating can be carried out by a known method such as a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, or a spray coating method. . Further, the drying can be carried out at 30 ° C to 150 ° C for 1 minute to 30 minutes using a hot air convection dryer or the like. In the conductive film 2, the conductive fiber and the organic conductor may coexist with a surfactant or a dispersion stabilizer.

The surface resistivity of the conductive film 2 and the photosensitive conductive film including the conductive film 2 can be adjusted by the amount of the conductive fibers. The larger the amount of the conductive fibers, the lower the surface resistivity of the conductive film, and the conductivity can be improved. On the other hand, the larger the amount of the conductive fibers, the lower the transmittance. In addition, as the amount of the conductive fibers increases, the light scattering by the conductive fibers becomes stronger, and the resolution tends to decrease.

In the present embodiment, the photosensitive layer may contain an ultraviolet absorber. For example, a conductive dispersion containing an ultraviolet absorber may be used to form a conductive film, and an ultraviolet absorber may be present in the conductive film, or the photosensitive resin layer may be present. UV absorber. For example, a conductive film formed by coating and drying a conductive dispersion containing an ultraviolet absorber on a support film or a photosensitive conductive film formed by forming a photosensitive resin layer on a conductive film may be contained. UV absorber.

Next, the photosensitive resin layer 3 will be described. The photosensitive resin layer 3 is formed of a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator. The photosensitive resin composition may also contain (D) an ultraviolet absorber.

(A) The binder polymer may, for example, be an acrylic resin, a styrene resin, an epoxy resin, a guanamine resin, a guanamine epoxy resin, an alkyd resin, a phenol resin, an ester resin, a urethane resin, An epoxy acrylate resin obtained by a reaction of an epoxy resin with (meth)acrylic acid, an acid-modified epoxy acrylate resin obtained by a reaction of an epoxy acrylate resin and an acid anhydride, or the like.

In the above, from the viewpoint of excellent alkali developability and film formability, an acrylic resin is preferably used, and it is more preferred that the acrylic resin has a (meth)acrylic acid and an alkyl (meth)acrylate. The monomer unit serves as a constituent unit. Here, the "acrylic resin" means a polymer mainly having a monomer unit derived from a polymerizable monomer having a (meth) acrylonitrile group.

The acrylic resin can be produced by radical polymerization of a polymerizable monomer having a (meth) acrylonitrile group.

Examples of the polymerizable monovalent body having a (meth) acrylonitrile group include acrylamide such as diacetone acrylamide; alkyl (meth) acrylate; 2-hydroxyalkyl (meth) acrylate; Tetrahydrofurfuryl acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate (meth)acrylate such as 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate; (meth)acrylic acid, α- (meth)acrylic acid such as bromine (meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl (meth)acrylic acid, or β-styryl (meth)acrylic acid.

The acrylic resin may also be produced by a styrene derivative, acrylonitrile, vinyl-n-butyl ether, etc., in addition to the polymerizable unitary body having a (meth) acrylonitrile group as described above. Ethyl alcohol esters; maleic acid; maleic anhydride; maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monoisopropyl ester, etc. Acid monoester; fumaric acid; cinnamic acid; α-cyanocinnamic acid; itaconic acid;

Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and hexyl (meth)acrylate. And (heptyl)methacrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, and the like.

The (A) binder polymer preferably has a carboxyl group from the viewpoint of improving alkali developability. The polymerizable monomer having a carboxyl group may, for example, be (meth)acrylic acid as described above.

The ratio of the carboxyl group of the (A) binder polymer is preferably from 10% by mass to 50% by mass, more preferably, based on the ratio of the polymerizable monomer having a carboxyl group to the total polymerizable unit to be used. It is 12% by mass to 40% by mass, particularly preferably 12% by mass to 30% by mass, particularly preferably 12% by mass to 25% by mass. In terms of excellent alkali developability, it is preferably 10% by mass or more, and is preferably 50% by mass or less from the viewpoint of excellent alkali resistance. (A) The binder polymer is preferably a binder polymer having a structural unit based on (meth)acrylic acid, a structural unit based on methyl (meth) acrylate or a structural unit based on ethyl (meth) acrylate. More preferably, it is a binder polymer having a structural unit based on (meth)acrylic acid, a structural unit based on methyl (meth) acrylate, and a structural unit based on ethyl (meth)acrylate.

The weight average molecular weight of the (A) binder polymer is preferably from 5,000 to 300,000, more preferably from 20,000 to 150,000, and still more preferably from 30,000 to 100,000, from the viewpoint of achieving a balance between mechanical strength and alkali developability. The weight average molecular weight is preferably 5,000 or more in terms of excellent developer resistance. Further, from the viewpoint of development time, it is preferably 300,000 or less. In the present specification, the weight average molecular weight is a value obtained by conversion using a gel permeation chromatography (GPC) and a standard curve prepared using standard polystyrene.

The acid value of the (A) binder polymer is preferably from 75 mgKOH/g to 200 mgKOH/g, more preferably from 75 mgKOH/g to 150 mgKOH/g, and particularly preferably 75, from the viewpoint of excellent pattern formability. From mgKOH/g to 120 mgKOH/g, particularly preferably from 78 mgKOH/g to 120 mgKOH/g.

(A) The acid value of the binder polymer can be determined in the following manner. First, 1 g was accurately weighed as a binder polymer for the measurement of the acid value. 30 g of acetone was added to the precisely weighed binder polymer to dissolve it evenly. Then, an appropriate amount of phenolphthalein as an indicator was dropped into the solution, and titration was carried out using a 0.1 N aqueous KOH solution. Then, the acid value was calculated according to the following formula. Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100) wherein Vf represents the titer (mL) of the aqueous KOH solution, and Wp represents the weight (g) of the solution containing the measured binder polymer, and I represents The proportion (% by mass) of the nonvolatile matter in the solution containing the measured binder polymer. In addition, when the binder polymer is used in a state of being mixed with a volatile component such as a synthetic solvent or a diluting solvent, it may be heated in advance at a temperature higher than the boiling point of the volatile component by 10 ° C or more before accurate weighing. After an hour to 4 hours, the volatile value was removed and the acid value was measured.

The (B) photopolymerizable compound will be described. The photopolymerizable compound preferably has an ethylenically unsaturated bond.

The photopolymerizable compound having an ethylenically unsaturated bond may, for example, be 2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl)propane, 2,2-bis(4-( Bisphenol A such as (meth)acryloxypolypropoxy)phenyl)propane and 2,2-bis(4-((meth)propenyloxypolyethoxypolypropoxy)phenyl)propane Di(meth)acrylate compound; polyalkylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene polypropylene glycol di(meth)acrylate, etc. Acrylate; trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tris(meth)acrylate, trishydroxyl Trimethylolpropane (meth) acrylate such as propane triethoxy tri(meth) acrylate; tetramethylol methane tri(meth) acrylate, tetramethylol methane tetra(meth) acrylate Di-pentaerythritol (meth) acrylate such as ester, tetramethylol methane (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane monomer Wait.

Among them, trimethylolpropane (meth) acrylate or dipentaerythritol (meth) acrylate is preferably used, and trimethylolpropane (meth) acrylate is more preferably used.

The content ratio of the (B) photopolymerizable compound is preferably from 30% by mass to 80% by mass, and more preferably from 40% by mass to 70% by mass, based on 100% by mass of the total of the binder polymer and the photopolymerizable compound. In view of being excellent in the coating property of the photocurable resin composition and the photosensitive resin composition, it is preferably 30% by mass or more, and is excellent in storage stability when it is wound as a film. 80% by mass or less.

The (C) photopolymerization initiator will be described. The photopolymerization initiator is not particularly limited as long as it selects the wavelength of light of the exposure machine to be used and the wavelength necessary for exhibiting the function. Examples of the photopolymerization initiator include benzophenone, N, N, N', N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N, N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-di Methylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1 Aromatic ketone; benzoin ether compound such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether; benzoin compound such as benzoin, methyl benzoin, ethyl benzoin; 1,2-octanedione-1-[4-(phenylthio) Phenyl]-2-(O-benzylidene hydrazide), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl] An oxime ester compound such as 1-(O-ethinylhydrazine); a benzyl derivative such as benzyldimethylketal; a phosphine oxide compound or an oxazole compound.

Among these compounds, the photopolymerization initiator is preferably an oxime ester compound or a phosphine oxide compound in terms of transparency and pattern forming ability in the case where the photosensitive layer is a film (for example, 10 μm or less).

Examples of the oxime ester compound include compounds represented by the following formula (C-1) and formula (C-2). From the viewpoint of quick-curing property and transparency, a compound represented by the following formula (C-1) is preferred. [Chemical 1] In the above formula (C-1), R ¹ represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms. R ^{1 is} preferably an alkyl group having 3 to 9 carbon atoms. Further, as long as the effects of the present invention are not inhibited, a substituent may be added to the aromatic ring in the above formula (C-1). The substituent may, for example, be a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

[Chemical 2] In the above formula (C-2), R ² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ³ represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms; ⁴ represents an alkyl group having 1 to 12 carbon atoms, and R ⁵ represents an alkyl group or an aryl group having 1 to 20 carbon atoms. P1 represents an integer of 0 to 3. When p1 is 2 or more, a plurality of R ^{4 's} may be the same or different. Further, the carbazole structure may have a substituent insofar as it does not inhibit the effects of the present invention. The substituent may, for example, be a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

In the above formula (C-2), R ² or R ^{4 is} preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms. base.

In the above formula (C-2), R ^{3 is} preferably an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 4 to 15 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, or carbon. The cycloalkyl group having 4 to 10 is particularly preferably a methyl group or an ethyl group.

In the above formula (C-2), R ^{5 is} preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 16 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or a carbon number of 6 to 6 carbon atoms. The aryl group of 14 is particularly preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

The compound represented by the above formula (C-1) is exemplified by 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoguanidinopurine). It can be obtained commercially as IRGACURE OXE 01 (manufactured by BASF). The compound represented by the above formula (C-2) may, for example, be ethyl ketone, 1-[9-ethyl-6-(2-methylbenzomethyl)-9H-indazol-3-yl]- , 1-(O-ethinylhydrazine), etc., can be commercially obtained as IRGACURE OXE 02 (manufactured by BASF).

Examples of the phosphine oxide compound include compounds represented by the following formula (C-3) and formula (C-4). From the viewpoint of quick-curing property and transparency, a compound represented by the following formula (C-3) is preferred.

[Chemical 3]

In the above formula (C-3), R ⁶ , R ⁷ and R ⁸ each independently represent an alkyl group or an aryl group having 1 to 20 carbon atoms. In the formula (C-4), R ⁹ , R ¹⁰ and R ¹¹ each independently represent an alkyl group or an aryl group having 1 to 20 carbon atoms.

In the case where R ⁶ , R ⁷ or R ⁸ in the formula (C-3) is an alkyl group having 1 to 20 carbon atoms, and R ⁹ or R ^{10 in} the formula (C-4) or When R ¹¹ is an alkyl group having 1 to 20 carbon atoms, the alkyl group may be linear, branched or cyclic, and the alkyl group preferably has 5 to 10 carbon atoms.

In the case where R ⁶ , R ⁷ or R ⁸ in the formula (C-3) is an aryl group, and R ⁹ , R ¹⁰ or R ^{11 in} the formula (C-4) is an aryl group In this case, the aryl group may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.

Among these, the above formula (C-3) is preferably R ⁶ , R ⁷ and R ⁸ are an aryl group. Further, the above formula (C-4) is preferably such that R ⁹ , R ¹⁰ and R ¹¹ are an aryl group.

The compound represented by the above formula (C-3) is preferably 2, 4 in terms of the transparency of the formed conductive pattern and the pattern forming ability when the film thickness is reduced (for example, 10 μm or less). 6-Trimethylbenzimidyl-diphenyl-phosphine oxide. 2,4,6-Trimethylbenzylidene-diphenyl-phosphine oxide is commercially available, for example, as LUCIRIN TPO (manufactured by BASF).

The compound represented by the above formula (C-4) is preferably double (2) in terms of the transparency of the formed conductive pattern and the pattern forming ability when the film thickness is reduced (for example, 10 μm or less). 4,6-Trimethylbenzylidene)-phenyl-phosphine oxide. Bis(2,4,6-trimethylbenzylidene)-phenyl-phosphine oxide can be commercially used, for example, as Irgacure 819 (manufactured by BASF). Obtain.

In addition to the oxime ester compound and the phosphine oxide compound, the compound having good transparency and pattern forming ability in the case of thinning the photosensitive layer is preferably 2,2-dimethoxy-1,2-diphenylethyl. Alkan-1-one. 2,2-Dimethoxy-1,2-diphenylethane-1-one can be commercially used, for example, as Irgacure 651 (manufactured by BASF) Obtain.

(C) Photopolymerization initiator is particularly preferably 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoguanidinopurine), ethyl ketone, 1 -[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), 2,4,6-trimethyl Benzobenzyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenyl-phosphine oxide, or 2,2-dimethoxy-1,2- Any of diphenylethane-1-one.

The content ratio of the photopolymerization initiator is preferably from 0.1 part by mass to 20 parts by mass, more preferably from 1 part by mass to 10 parts by mass, even more preferably 100 parts by mass based on the total of the binder polymer and the photopolymerizable compound. 1 part by mass to 5 parts by mass. In terms of excellent photosensitivity, it is preferably 0.1 part by mass or more, and is preferably 20 parts by mass or less from the viewpoint of excellent photocurability.

The (D) ultraviolet absorber will be described. From the viewpoint of absorbing the scattered light by the conductive fibers, the (D) ultraviolet absorber preferably has an excellent absorption ability of ultraviolet rays having a wavelength of 400 nm or less, and is preferably a wavelength from the viewpoint of improving transparency. Less absorption of visible light above 400 nm. Specifically, a material having a maximum absorption wavelength in a wavelength region of 250 nm or more and 400 nm or less is in conformity.

By including (D) the ultraviolet absorber in the photosensitive layer, the scattered light caused by the conductive fibers can be absorbed, and the halation can be suppressed, whereby the decrease in the resolution can be sufficiently suppressed. Further, the components contained in the conductive film and the conductive pattern are decomposed by ultraviolet light to generate an acid (for example, acetic acid or the like), and the conductive fibers are corroded or deteriorated, whereby the electric resistance of the conductive pattern rises. When the ultraviolet absorber is contained in the photosensitive layer, the increase in electric resistance can be suppressed.

(D) The ultraviolet absorber may, for example, be an oxybenzophenone compound, a triazole compound, a benzotriazole compound, a salicylate compound, a benzophenone compound, a diphenyl acrylate compound, or a cyanoacrylate compound. A diphenyl cyanoacrylate compound, a nickel stearate compound, or the like. Among these compounds, a diphenyl cyanoacrylate compound, a cyanoacrylate compound, or a diphenyl acrylate compound is preferable.

(D) The ultraviolet absorber is preferably a compound having a reactive group, and more preferably a compound having a thermally polymerizable group or a photopolymerizable group. The effect of the present invention can be expected to be improved by increasing the content of the ultraviolet absorber. However, in the case where the content of the ultraviolet absorber is increased, the ultraviolet absorber may permeate out from the resin hardened after patterning (exudation ( Bleed out)) The possibility. The bleed out of the ultraviolet absorber is less likely to cause deterioration in transparency of the cured resin, deterioration of optical characteristics such as turbidity, and the like. Further, when the content of the ultraviolet absorber is increased, there is a possibility that the ultraviolet absorber which does not enter the cured resin is adsorbed on the surface of the conductive fiber. The adsorption of the ultraviolet absorber on the conductive fibers is a cause of an increase in the resistance value of the conductive film, which is not preferable. In contrast, in the case where the ultraviolet absorber has a reactive group, the ultraviolet absorber is fixed to the resin cured material during patterning (for example, it is firmly bonded by covalent bonding in the network of the cured resin) The connection, incorporation, thereby suppressing the permeation (exudation) of the ultraviolet absorber or the movement of the ultraviolet absorber in the cured product of the resin. Therefore, even if the content of the ultraviolet absorber is increased, the increase in the resistance value due to the adsorption of the ultraviolet absorber on the surface of the conductive fiber can be suppressed.

Examples of the thermally polymerizable group include an epoxy group, a glycidyl group, an isocyanate group, an ethynyl group, a maleimide group, and an oxetanyl group. Examples of the photopolymerizable group include a (meth) acrylonitrile group, an allyl group, a maleimide group, and the like. The thermally polymerizable group and the photopolymerizable group are not limited to the above examples. In the present embodiment, the ultraviolet absorber having a reactive group which is generated by heat or light and which can be polymerized by an active radical, an acid or an alkali can be used without particular limitation, and can suppress ultraviolet rays. The permeation (exudation) of the absorbent or the adsorption on the surface of the conductive fiber.

Among the compounds having a thermopolymerizable group or a photopolymerizable group, it is particularly preferable to have a (meth) group as a photopolymerizable group in terms of ease of availability and stability in the photosensitive conductive film before curing. A propylene sulfhydryl compound. Examples of such an ultraviolet absorber include 2-[2-hydroxy-5-[2-(methacryloxy)ethyl]phenyl]-2H which is a benzotriazole compound having a (meth)acryl fluorenyl group. - benzotriazole. 2-[2-Hydroxy-5-[2-(methacryloxy)ethyl]phenyl]-2H-benzotriazole can be produced, for example, as RUBA-93 (Otsuka Chemical Co., Ltd.) , trade name) or DAINSORB T-31 (made by Daiwa Kasei Co., Ltd., trade name) and obtained commercially.

(D) The ultraviolet absorber is preferably a polymer type ultraviolet absorber. The polymer type ultraviolet absorber is an ultraviolet absorber obtained by polymerizing the compound having a thermally reactive group or a photopolymerizable group. The polymer type ultraviolet absorber is a material having one or more ultraviolet absorbing sites in the molecule and is a material having a large molecular weight. The molecular weight of the "polymer type" is not clearly defined. In the present specification, the ultraviolet absorber having a weight average molecular weight of 3,000 or more is referred to as a polymer type ultraviolet absorber. The bleeding of the polymer type ultraviolet absorber is suppressed as compared with the low molecular weight ultraviolet absorber. Further, adsorption of the polymer type ultraviolet absorber on the surface of the conductive fiber is difficult to suppress. Thereby, a large amount of the ultraviolet absorber can be contained in the photosensitive conductive film, and the influence of the scattered light by the conductive fiber can be more effectively reduced.

The polymer type ultraviolet ray absorbing agent is preferably one in which the compound having a polymerizable reactive group as a raw material is easy to be obtained, the ease of adjustment of the molecular weight, and the copolymerizable component of the polymer can be widely selected. A polymer obtained by polymerizing a compound having a (meth)acryl fluorenyl group as a photopolymerizable group as a raw material.

As a polymer type ultraviolet absorber, the solvent is an RSA series (for example, RSA-0124, RSA-0151, and RSA-0191H; both manufactured by Shannan Synthetic Chemical Co., Ltd.) and a solvent-based PUVA series (for example, PUVA-30M-50BA, PUVA-30M-30T and PUVA-50M-50K; all manufactured by Daiwa Kasei Co., Ltd., solvent RSU series (eg RSU-0017 and SG-864; both manufactured by Daiwa Kasei Co., Ltd., and the water-based RWU series (for example, MW-022, RWU-0001, and RWU-0109; all manufactured by Daiwa Kasei Co., Ltd.) are commercially available. In addition, the water system Newcoat UVA series (eg Newcoat UVA-101, Newcoat UVA-102, Newcoat UVA-103 and Newcoat UVA) -104), solvent system Vanalesin UVA series (for example: Vanaresin UVA-5080, hydroxyl-introduced Vanaresin UVA-5080 (OHV20), Banalesin (Vanaresin) UVA-55T, high hydroxyl value type Vanaresin UVA-55MHB, Vanaresin UVA-7075, hydroxyl-introduced Vanaresin UVA-7075 (OHV20) and Vanaresin (UVA-73T) and the like are commercially available from New Nakamura Chemical Industry Co., Ltd. In addition, the solvent-based UVA series (for example, UVA-935LH and UVA-1935LH) and the water-based UVA series (for example, UVA-700 and UVA-1700) are commercially available from BASF.

The weight average molecular weight of the polymer type ultraviolet absorber is preferably 300,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less, from the viewpoint of solubility in a solvent and compatibility with a photosensitive resin composition. . In addition, from the viewpoint of preventing bleeding from the photosensitive conductive film and the cured film thereof, it is preferably 3,000 or more, more preferably 5,000 or more, and still more preferably 10,000 or more. From the viewpoints of solubility in a solvent, compatibility with a photosensitive resin composition, and balance of prevention of bleeding prevention, it is preferably 3,000 to 300,000, more preferably 5,000 to 150,000, and particularly preferably 10,000. 100000. Further, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted according to a standard curve prepared using standard polystyrene.

The content of the (D) ultraviolet absorber is preferably from 0.1 part by mass to 30 parts by mass, more preferably from 1 part by mass to 20 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). It is preferably 2 parts by mass to 10 parts by mass.

The content of the (D) ultraviolet absorber is preferably 0.1 part by mass or more in terms of effectively suppressing light scattering by the conductive fiber and having excellent resolution. In addition, the ultraviolet absorbing agent is prevented from oozing out from the photosensitive conductive film and the cured film thereof, the adsorption on the surface of the conductive fiber is suppressed, or the absorption of the surface of the photosensitive layer is suppressed from being increased when the actinic ray is irradiated. In the aspect where the internal photohardening is insufficient, it is preferably 30 parts by mass or less.

The method of including the (D) ultraviolet absorber in the photosensitive layer is usually a method of adding the composition to the photosensitive resin composition in advance, but the present invention is not limited to the internal addition. Other methods of including the ultraviolet absorber in the photosensitive layer include, for example, a method of internally adding an ultraviolet absorber to the conductive fiber dispersion; and exposing the film containing the conductive fiber formed on the support film to the liquid containing the ultraviolet absorber After that, the method of re-drying to form a conductive film or the like is performed. In order to uniformly contain a sufficient amount of the ultraviolet absorber in the photosensitive resin composition, it is possible to effectively suppress deterioration or disconnection of the conductive fibers by ultraviolet rays, and it is preferable to add the film to the photosensitive resin composition in advance.

In the photosensitive resin composition of the present embodiment, it may be contained in an amount of from 0.01 part by mass to 20 parts by mass per 100 parts by mass of the total amount of the component (A) and the component (B). A compatibility imparting agent, a leveling agent, a plasticizer, a filler, an antifoaming agent, a flame retardant, a stabilizer, an antioxidant, a perfume, a thermal crosslinking agent, a polymerization inhibitor, and the like.

The photosensitive resin layer 3 can be dissolved in methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol A solvent such as methyl ether or a solution of a photosensitive resin composition in the mixed solvent is applied onto the support film 1 on which the conductive film 2 is formed, and dried. In this case, in order to prevent the diffusion of the organic solvent in the step described later, the amount of the residual organic solvent in the photosensitive resin layer after drying is preferably 2% by mass or less.

The application of the photosensitive resin layer 3 can be performed by, for example, a roll coating method, a slanting wheel coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, a spray coating method, or the like. The way to proceed. After the application, the drying for removing the organic solvent or the like can be carried out at 70 ° C to 150 ° C for about 5 minutes to 30 minutes using a hot air convection dryer or the like.

The thickness of the photosensitive resin layer 3 varies depending on the application, and is preferably 1 μm to 50 μm, more preferably 1 μm to 15 μm, and still more preferably 1 μm to 10 μm, in terms of thickness after drying. When the thickness is less than 1 μm, the coating tends to be difficult. When the thickness is more than 50 μm, the sensitivity is insufficient due to the decrease in light transmission, and the photocurability of the transferred photosensitive resin layer is lowered. tendency. The thickness of the layer (cured film) obtained by curing the photosensitive resin layer 3 is also preferably in the above range.

In the photosensitive conductive film used in the present embodiment, the laminated body of the conductive film 2 and the photosensitive resin layer 3 is preferably 400 nm when the total thickness of the two layers is 1 μm to 10 μm. The minimum value of the visible light transmittance in the above wavelength range of 700 nm or less is 85% or more, and more preferably 90% or more. When the conductive film and the photosensitive resin layer satisfy the above conditions, the visibility of the display panel or the like is further improved.

The surface resistivity of the conductive film or the conductive pattern is preferably 1000 Ω/□ or less, and more preferably 500 Ω/□ or less, from the viewpoint that the photosensitive conductive film used in the present embodiment is effectively used as a transparent electrode. Especially preferred is 300 Ω/□ or less. The surface resistivity can be adjusted, for example, by the concentration or coating amount of the dispersion of the conductive fiber or the organic conductor.

In the photosensitive conductive film used in the present embodiment, the protective film 5 may be laminated so as to be in contact with the surface of the photosensitive resin layer 3 on the side opposite to the support film 1 side.

As the protective film 5, a polymer film having heat resistance and solvent resistance such as a polyethylene terephthalate film, a polypropylene film, or a polyethylene film can be used. Further, a polymer film similar to the above-described support film may be used as the protective film 5.

When the protective film is peeled off and laminated on the substrate from the photosensitive resin layer 3 side, in order to easily peel the protective film from the photosensitive layer, the adhesion between the protective film 5 and the photosensitive layer 4 is preferably smaller. The adhesion between the photosensitive layer 4 and the support film 1. On the other hand, in the case where the support film 1 is peeled off and laminated on the substrate from the side of the conductive film 2, in order to easily peel the support film from the photosensitive layer, the adhesion between the protective film 5 and the photosensitive layer 4 is higher. It is preferably greater than the adhesion between the photosensitive layer 4 and the support film 1.

In the protective film 5, the number of fish eyes having a diameter of 80 μm or more contained in the protective film is preferably 5/m ² or less. When the film is produced by kneading, extrusion, biaxial stretching, casting, or the like, the "fish eye" is obtained by introducing a foreign matter, an undissolved product, an oxidized degradation product, or the like into the film.

The thickness of the protective film 5 is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, still more preferably from 5 μm to 30 μm, particularly preferably from 15 μm to 30 μm. When the thickness of the protective film is less than 1 μm, the protective film tends to be broken during lamination, and when it exceeds 100 μm, the winding property of the photosensitive conductive film tends to decrease.

<Method for Forming Conductive Pattern and Substrate with Conductive Pattern> The method for forming a conductive pattern of the present invention includes the step of transferring the photosensitive layer of the photosensitive conductive film of the present invention onto a substrate (also referred to as a lamination step) And an exposure step of patterning the actinic layer on the photosensitive layer transferred onto the substrate; and developing a step of forming a conductive pattern by removing the unexposed portion of the photosensitive layer. Hereinafter, a method of forming the conductive pattern of the present invention will be described using a drawing.

3(a), 3(b), and 3(c) are schematic cross-sectional views for explaining an embodiment of a method of forming a conductive pattern using a photosensitive conductive film. The method for forming a conductive pattern according to the present embodiment includes a lamination step (Fig. 3(a)), peeling off the support film 1, and laminating the photosensitive conductive film 10 on the substrate 20 in such a manner that the conductive layer 2 is closely adhered. And a patterning step (Fig. 3 (b) and Fig. 3 (c)), the conductive pattern is formed by exposing and developing the photosensitive layer 4 on the substrate. The patterning step includes an exposure step of irradiating the predetermined portion of the photosensitive layer 4 of the protective film 5 with an actinic ray (Fig. 3(b)), and then removing the protective film 5 to develop the developing layer 4 (Fig. 3(c)). The substrate 40 with the conductive pattern is thus obtained.

4(a), 4(b) and 4(c) are schematic cross-sectional views for explaining another embodiment of a method of forming a conductive pattern using a photosensitive conductive film. The method of forming the conductive pattern of the present embodiment and the method of forming the conductive pattern are different in that the photosensitive layer 3 is laminated so that the photosensitive resin layer 3 is adhered to the substrate 20 when the photosensitive layer is laminated. In other words, the photosensitive conductive film 10 including the support film 1 , the conductive film 2 , and the photosensitive resin layer 3 is prepared, and the photosensitive resin layer 3 of the photosensitive conductive film 10 is adhered to the substrate 20 so as to be on the substrate 20 . The photosensitive layer is laminated (Fig. 4(a)). Then, the actinic resin layer 3 is irradiated with actinic rays L in a pattern-like manner (FIG. 4(b)), and after the support film 1 is peeled off, the unhardened portion (unexposed portion) is removed by development. Thereby, the conductive pattern 2a is formed (Fig. 4(c)).

The method for forming the conductive pattern includes a step of laminating the photosensitive conductive film of the present invention on a substrate in such a manner that a photosensitive resin layer is adhered; and an exposure step in a state with the support film, a predetermined portion of the photosensitive resin layer on the material is irradiated with actinic rays; then the support film is peeled off; and a developing step is performed to develop a conductive pattern by developing the exposed photosensitive resin layer. By following these steps, a substrate 41 with a conductive pattern comprising a patterned conductive pattern on a substrate is obtained. The conductive pattern thus obtained has the thickness of the resin-hardened pattern 3b in addition to the thickness of the conductive pattern 2a. These thicknesses become the step difference Hb with the substrate, and if the step is large, it is difficult to obtain smoothness required for a display or the like. Further, if the step is large, it is easy to visually recognize the conductive pattern. Therefore, it is only necessary to use it separately from the method shown in FIGS. 5(a), 5(b), 5(c), and 5(d) depending on the application.

5(a), 5(b), 5(c), and 5(d) are schematic cross-sectional views for explaining another embodiment of a method of forming a conductive pattern using a photosensitive conductive film. After the first exposure step (Fig. 5(b)) of irradiating the predetermined portion of the photosensitive layer 4 having the support film 1 with the actinic ray (Fig. 5(b)), the following second exposure step is included (Fig. 5(c)): the peeling support film 1 Thereafter, a part or all of the exposed portion and the unexposed portion in the first exposure step are irradiated with actinic rays in the presence of oxygen. The second exposure step is preferably carried out in the presence of oxygen, for example in air. In addition, it may be a condition in which the oxygen concentration is increased.

In the developing step of the method of forming the conductive pattern of FIGS. 5(a), 5(b), 5(c), and 5(d), the exposed photosensitive resin layer 3 in the second exposure step is not The fully hardened surface portion is removed. Specifically, the surface portion of the photosensitive resin layer 3 that is not sufficiently cured, that is, the surface layer containing the conductive film 2 is removed by the wet phenomenon. Thereby, a resin hardened layer having no conductive film is provided on the substrate 20 together with the conductive pattern, and the substrate 42 with the conductive pattern is obtained, and the conductive pattern can be reduced as compared with the case where only the conductive pattern is provided on the substrate. The step Ha.

The method for forming the conductive pattern includes the step of laminating the photosensitive conductive film of the present invention on a substrate in such a manner that the photosensitive resin composition is adhered; the first exposing step includes sensitizing the film on the substrate a photosensitive layer and a photosensitive layer of a conductive film provided on a surface of the photosensitive resin layer opposite to the substrate, irradiating actinic rays in a pattern; and a second exposure step, in the presence of oxygen, A part or all of the unexposed portion in at least the first exposure step of the photosensitive layer irradiates the actinic ray; and a developing step of forming the conductive pattern by developing the photosensitive layer after the second exposing step. The conductive pattern 2a formed on the resin hardened layer 3a of the conductive pattern thus obtained can be reduced in the step Ha.

Examples of the substrate include a glass substrate, a plastic substrate such as polycarbonate, and the like. The substrate preferably has a minimum light transmittance of 85% or more in a wavelength range of 400 nm to 700 nm.

The laminating step is performed, for example, by removing the protective film or the support film in the presence of a protective film or a support film, and heating the photosensitive conductive film while heating the photosensitive resin layer or the conductive film side. Crimped onto the substrate. In terms of adhesion and follow-up, the work is preferably carried out under reduced pressure. In the lamination of the photosensitive conductive film, it is preferred to heat the photosensitive layer or the substrate to 70 ° C to 130 ° C, and the pressure of the bonding is preferably set to about 0.1 MPa to 1.0 MPa (1 kgf / cm ² to 10 kgf / cm). ² or so), but there are no special restrictions on these conditions. Further, when the photosensitive layer is heated to 70 to 130 ° C as described above, it is not necessary to preheat the substrate in advance, but in order to further improve the layering property, the substrate may be subjected to preheat treatment.

In the exposure step of irradiating actinic rays to a predetermined portion of the photosensitive layer on the substrate in a state with a support film, the exposure method may be exemplified by a negative or positive mask pattern called an artwork. A method of irradiating actinic rays in a shape (mask exposure method). The light source of the actinic ray is a well-known light source.

The exposure amount in the exposure step differs depending on the apparatus used and the composition of the photosensitive resin composition, and is preferably 5 mJ/cm ² to 1000 mJ/cm ² , more preferably 10 mJ/cm ² to 200 mJ/cm. ² . In terms of excellent photocurability, it is preferably 10 mJ/cm ² or more, and is preferably 1000 mJ/cm ² or less in terms of resolution. The exposure step may be carried out in two stages, or the second stage may be carried out at 100 mJ/cm ² to 10000 mJ/cm ² after the first stage of the exposure.

The wet development is carried out by a known method such as spraying, shaking, scouring, scrubbing or scrubbing, using a developing solution corresponding to the photosensitive resin to be used, such as an aqueous alkaline solution, an aqueous developing solution, or an organic solvent developing solution.

As the developer, it is safe and stable to use an alkaline aqueous solution or the like, and the workability is good. The base of the alkaline aqueous solution is an alkali hydroxide such as a hydroxide of lithium, sodium or potassium, a carbonate such as a carbonate of lithium, sodium, potassium or ammonium or a hydrogencarbonate; an alkali metal such as potassium phosphate or sodium phosphate; Phosphate; alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate.

The alkaline aqueous solution used for development is preferably a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, an aqueous sodium hydroxide solution, an aqueous sodium tetraborate solution or the like. The concentration of the alkaline aqueous solution is usually 0.1% by mass to 5% by mass. Further, the pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted in accordance with the developability of the photosensitive resin layer. Further, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution.

An aqueous developing solution containing water or an aqueous alkali solution and one or more organic solvents can be used. Here, the base contained in the aqueous alkali solution may be used in addition to the above-mentioned base: borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2- Amino-2-hydroxymethyl-1,3-propanediol, 1,3-diamino-2-propanol, morpholine and the like.

Examples of the organic solvent include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. , diethylene glycol monobutyl ether and the like.

The aqueous developing solution preferably has a concentration of the organic solvent of 2% by mass to 90% by mass, and the temperature can be adjusted according to the developability. Further, the pH of the aqueous developing solution is preferably reduced within a range in which the development of the resist can be sufficiently performed, and is preferably pH 8 to 12, more preferably pH 9 to 10. . Further, a small amount of a surfactant, an antifoaming agent, or the like may be added to the aqueous developing solution.

Examples of the organic solvent-based developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ. - Butyrolactone and the like. In order to prevent ignition, the organic solvent is preferably added in an amount of from 1% by mass to 20% by mass.

Examples of the development method include a dipping method, a liquid coating method, a high pressure spraying method, brushing, and slapping. Among these methods, from the viewpoint of improving the resolution, it is preferable to use a high pressure injection method.

In the method for forming a conductive pattern of the present invention, after the development, the conductive pattern may be further hardened by heating at about 60 ° C to 250 ° C or exposure of about 0.2 J/cm ² to 10 J/cm ² as needed. .

According to the method for forming a conductive pattern of the present invention, a transparent conductive pattern can be easily formed on a substrate such as glass or plastic without forming a resist layer like an inorganic film such as ITO.

The substrate with a conductive pattern of the present invention is obtained by the method of forming the conductive pattern, and the surface resistivity of the conductive film or the conductive pattern is preferably 1000 from the viewpoint of being effective and transparent as a transparent electrode. Below Ω/□, it is more preferably 500 Ω/□ or less, and particularly preferably 300 Ω/□ or less. The surface resistivity can be adjusted, for example, by the concentration or coating amount of the dispersion of the conductive fiber or the organic conductor.

The substrate with a conductive pattern of the present invention preferably has a minimum visible light transmittance of 80% or more, more preferably 85% or more, and particularly preferably 90% or more in a wavelength range of 400 nm or more and 700 nm or less. When the conductive pattern substrate satisfies the above conditions, the visibility in the display panel or the like is further improved. The light transmittance can be adjusted by the concentration and application amount of the dispersion of the conductive fiber or the organic conductor. Further, the transmittance can be adjusted by the shape (fiber diameter, and fiber length) of the conductive fiber. The finer the fiber diameter, the higher the transmittance.

<Touch Panel Sensor> The method for forming a conductive pattern of the present invention and the substrate with a conductive pattern can be preferably used, for example, as a transparent electrode of a capacitive touch panel, and a capacitive touch panel. Sensor.

6 is a schematic plan view showing an example of a capacitive touch panel sensor. FIG. 6 shows an example of a capacitive touch panel sensor including a transparent substrate 101, a transparent electrode (X position coordinate) 103, and a transparent electrode (Y position coordinate) 104 in the touch screen 102. The transparent electrode 103 and the transparent electrode 104 may exist on the same plane, or may be laminated on the transparent substrate 101 or may be disposed so as to sandwich the transparent substrate 101.

The transparent electrode 103 and the transparent electrode 104 of the capacitive touch panel have lead wires (not shown) for connecting to a control circuit of a drive element circuit that controls an electrical signal.

At least one of the transparent electrodes of the touch panel sensor of the present embodiment is formed using the photosensitive conductive film of the present invention. In this case, the other transparent electrode may be previously formed on the transparent substrate by a known method using a transparent conductive material. [Examples]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

The components used in the examples and comparative examples are as follows. (B) Component · Trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "TMPTA")

(C) component · 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzhydrylhydrazine)] (Manufactured by BASF) "OXE-01") · 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide (Manufactured by BASF), trade name "LUCIRIN TPO") 2,2-Dimethoxy-1,2-diphenylethane-1-one (Manufactured by BASF) under the trade name "Irgacure 651"

(D) Component · Ethyl 2-cyano-3,3-diphenylacrylate (manufactured by Shipro Kasei Co., Ltd., trade name "SEESORB 501") · 2-[ 2-Hydroxy-5-[2-(methacryloxy)ethyl]phenyl]-2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd. under the trade name "RUBA-93") ·Polymer type UV absorber (made by Daiwa Kasei Co., Ltd., trade name "PUBA-50M-50K")

·Carbon nanotubes (high pressure carbon (Hipco) single-layer carbon nanotubes, high purity, manufactured by Uniji (Unidym)) · Dodecyl-pentaethylene glycol ( Wako Pure Chemical Co., Ltd.

(Other Ingredients) · Octamethylcyclotetraoxane (Manufactured by Toray Dow Corning Co., Ltd., trade name "SH-30") (Leveling Agent) · Methyl Ethyl Ketone (Dongyan Chemical) (stock) manufacturing) (solvent)

Production Example 1 <Preparation of Silver Fiber Dispersion (Conductive Fiber Dispersion (Coating Liquid for Conducting Film Formation))> [Preparation of Silver Fiber by Polyol Method] 500 mL of Ethylene was added to a 2000 mL three-necked flask The alcohol was heated to 160 ° C using an oil bath while stirring under a nitrogen atmosphere with a magnetic stirrer. Thereto, a separately prepared solution 1 (a solution obtained by dissolving 2 mg of PtCl ₂ in 50 mL of ethylene glycol) was added dropwise. After 4 minutes to 5 minutes, solution 2 (a solution obtained by dissolving 5 g of AgNO ₃ in 300 mL of ethylene glycol) and solution 3 (5 g) were added dropwise from each dropping funnel over 1 minute. A polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight: 58,000) dissolved in 150 mL of ethylene glycol), and the reaction solution was stirred at 160 ° C for 60 minutes.

After the reaction solution was allowed to stand at 30 ° C or lower, it was diluted with acetone to 10 times. The diluted solution of the reaction solution was centrifuged at 2000 rpm for 20 minutes by a centrifugal separator, and the supernatant was decanted. Acetone was added to the precipitate, and after stirring, the mixture was centrifuged under the same conditions as described above, and acetone was decanted. Then, using centrifugal water, centrifugation was carried out twice in the same manner to obtain silver fibers. The obtained silver fiber was observed by an optical microscope as follows: the fiber diameter (diameter) was 30 nm, and the fiber length was 3 μm.

[Preparation of the silver fiber dispersion] In the pure water, the silver fiber obtained has a concentration of 0.2% by mass, and the dodecyl-pentaethylene glycol is dispersed at a concentration of 0.1% by mass. Thereby obtaining a silver fiber dispersion.

<Preparation of carbon nanotube dispersion> In pure water, a high-purity product of Unicomm's Hipco single-layer carbon nanotubes is dispersed to a concentration of 0.4% by mass, and will be used as a surfactant. The dodecyl-pentaethylene glycol was dispersed at a concentration of 0.1% by mass to obtain a carbon nanotube dispersion.

Production Example 2 <Preparation of a binder polymer (A1) solution> In a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer, (1) shown in Table 1 was placed, and the temperature was raised to 80 in a nitrogen atmosphere. °C. While maintaining the reaction temperature at 80 ° C ± 2 ° C, (2) shown in Table 1 was uniformly dropped for 4 hours. After the dropwise addition (2), stirring was continued at 80 ° C ± 2 ° C for 6 hours to obtain a binder polymer (A1) solution having a weight average molecular weight of 45,000 (solid content: 50% by mass). The acid value of the binder polymer (A1) was 78 mgKOH/g. Further, the glass transition temperature (Tg) was 60 °C.

[Table 1]

Production Example 3 <Preparation of a polymer type ultraviolet absorber (D1) solution> In a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer, (1) shown in Table 2 was placed, and the temperature was raised in a nitrogen atmosphere. To 80 ° C. While maintaining the reaction temperature at 80 ° C ± 2 ° C, (2) shown in Table 2 was uniformly dropped for 4 hours. After the dropwise addition (2), stirring was continued at 80 ° C ± 2 ° C for 6 hours to obtain a polymer type ultraviolet absorbent (D1) solution having a weight average molecular weight of 15,000 (solid content: 50% by mass). The polymer type ultraviolet absorber (D1) has an acid value of 0 mgKOH/g.

[Table 2]

The properties of the produced polymer solution were determined by the following methods.

(1) Weight average molecular weight The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) and converted using a standard curve of standard polystyrene. The conditions of GPC are shown below.

Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd., trade name) Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (above, manufactured by Hitachi Chemical Co., Ltd., trade name) Dissolution : Tetrahydrofuran measurement temperature: 40 ° C Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., trade name)

(2) Acid value The acid value was measured in the following manner. First, a solution of the binder polymer was heated at 130 ° C for 1 hour to remove volatile components to obtain a solid polymer. Next, after accurately weighing 1 g of the solid polymer, the accurately weighed polymer was placed in a conical flask, 30 g of acetone was added, and the solution was uniformly dissolved. Then, an appropriate amount of phenolphthalein as an indicator was added to the solution, and titration was carried out using a 0.1 N aqueous KOH solution. Then, the acid value was calculated according to the following formula. Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100) wherein Vf represents the titer (mL) of the aqueous KOH solution, Wp represents the mass (g) of the measured resin solution, and I represents the measured resin solution. The proportion (% by mass) of non-volatile components in the medium. Further, the acid value of the polymer type ultraviolet absorber (D1) was also calculated by the same operation.

(3) Glass transition temperature (Tg) The solution of the produced binder polymer was uniformly applied to a polyethylene terephthalate film (manufactured by Teijin DuPont Films Co., Ltd., trade name) On "Purex A53", it was dried by a hot air convection dryer at 90 ° C for 10 minutes to form a film of a binder polymer having a thickness of 40 μm after drying. Then, using an exposure machine having a high-pressure mercury lamp (manufactured by ORC Manufacturing Co., Ltd., trade name "EXM-1201"), the amount of irradiation energy is 400 mJ/cm ² (i-ray (wavelength is 365 nm) The measured value of the film was exposed to the film. The exposed film was heated on a hot plate at 65 ° C for 2 minutes, followed by heating at 95 ° C for 8 minutes, and then heated at 180 ° C for 60 minutes using a hot air convection dryer, self-polyethylene terephthalate. The film was peeled off, and the thermal expansion coefficient of the cured film when the temperature was raised at a temperature increase rate of 5 ° C/min was measured using TMA/SS6000 (manufactured by Seiko Instruments Co., Ltd.), and the inflection point obtained from the curve was obtained. Take the glass transfer temperature Tg.

Example 1 <Preparation of photosensitive conductive film V1> [Production of conductive film (conductive film of photosensitive conductive film) W1] The silver fiber dispersion obtained in the above Production Example 1 was uniformly distributed at 25 g/m ² It is applied to a 50 μm thick polyethylene terephthalate film (polyethylene terephthalate (PET) film, manufactured by Teijin Co., Ltd., trade name "G2-50"). The hot air convection dryer at 100 ° C was dried for 3 minutes to form a conductive film W1. The film thickness after drying of the conductive film was 0.1 μm.

[Preparation of Solution X1 of Photosensitive Resin Composition] The materials shown in Table 3 were mixed for 15 minutes in the amount shown in Table 3 using a stirrer to prepare a solution X1 of the photosensitive resin composition. The blending amount of the component (A) is the mass of the solid component.

[table 3]

[Preparation of Photosensitive Conductive Film V1] The solution X1 of the photosensitive resin composition was uniformly applied onto the conductive film W1, and dried by a hot air convection dryer at 100 ° C for 10 minutes to form a photosensitive resin layer. Then, the photosensitive resin layer was covered with a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name "NF-13") to obtain a photosensitive conductive film V1. The film thickness after drying of the photosensitive resin layer was 5 μm.

<Evaluation of Photosensitive Conductive Film V1> [Measurement of Light Transmittance of Photosensitive Conductive Film V1] The polyethylene film of the obtained photosensitive conductive film V1 was peeled off on a glass substrate having a thickness of 1 mm. For the contact of the photosensitive resin layer, a laminator (manufactured by Hitachi Chemical Co., Ltd., trade name "HLM-3000") was used, and the roll temperature was 110 ° C, the substrate feed rate was 1 m/min, and the crimping pressure was applied. (cylinder pressure) is 4 × 10 ⁵ Pa (by using a substrate having a thickness of 1 mm, a length of 10 cm × a width of 10 cm, and the linear pressure at this time is 9.8 × 10 ³ N/m), thereby laminating A substrate on which a photosensitive conductive film V1 including a support film is laminated on a glass substrate is prepared.

Then, for the photosensitive conductive film on the glass substrate, a parallel light exposure machine (manufactured by ORC Co., Ltd., EXM1201) was used, and the exposure amount was 5 × 10 ² J/m ² (i-ray) from the side of the support film. (measured value at a wavelength of 365 nm) to irradiate ultraviolet rays. Then, the support film was removed, and the ultraviolet ray was irradiated from the side of the conductive film by an exposure amount of 1 × 10 ⁴ J/m ² (i-ray (wavelength: 365 nm)) to obtain a photosensitive resin. A sample for transmittance measurement of a layer and a conductive film (photosensitive layer) (having a film thickness of 5.0 μm).

Then, for the obtained sample, an ultraviolet-visible spectrophotometer (manufactured by Hitachi Metro Service Co., Ltd., trade name "U-3310") was used to measure the ultraviolet light transmittance by measuring the wavelength range of 300 nm to 380 nm. The visible light transmittance was measured by measuring the wavelength range of 400 nm to 700 nm. Further, the transmittance of the photosensitive conductive film alone was measured using a glass substrate as a background.

The visible light transmittance of the obtained photosensitive conductive film was 99% at a wavelength of 700 nm, 99% at a wavelength of 550 nm, and 87% at a wavelength of 400 nm. The minimum visible light transmittance in the wavelength range of 400 nm or more and 700 nm or less is 87%, which ensures good transmittance. In addition, the UV transmittance was 71% at 380 nm and 15% at 300 nm. The maximum transmittance of ultraviolet light from 300 nm to 380 nm is 71%.

[Measurement of Surface Resistivity of Photosensitive Conductive Film V1] A sample for surface resistivity measurement in which a photosensitive conductive film V1 is laminated on a glass substrate is prepared in the same manner as the method of measuring the light transmittance of the photosensitive conductive film V1. . The surface resistivity of the sample was measured by a non-contact resistance measuring device (manufactured by Napson Co., Ltd., trade name "EC-80P"), and found to be 100 ± 5 Ω / □.

[Measurement of the sensitivity of the photosensitive conductive film V1] The polyethylene film of the photosensitive conductive film V1 was peeled off on the easy-contact surface of the PET film substrate (thickness: 50 μm, manufactured by Toyobo Co., Ltd., trade name "A4100"). A laminator (manufactured by Hitachi Chemical Co., Ltd., trade name "HLM-3000 type") was used to contact the photosensitive resin layer, and the roll temperature was 110 ° C, the substrate feed rate was 1 m/min, and the pressure was 1. Lamination was carried out under the conditions of a pressure (cylinder pressure) of 4 × 10 ⁵ Pa to prepare a film substrate on which a photosensitive conductive film V1 containing a support film was laminated on a PET film substrate.

Then, the support film 1 of the photosensitive conductive film on the film substrate was sealed with a 41-step ladder (manufactured by Hitachi Chemical Co., Ltd.) as a mask, and a parallel light exposure machine was used.珂(ORC), manufactured by ORC, manufactured under the trade name "EXM1201", exposed from the support film 1 side through a mask. The exposure amount was set to 4 × 10 ² J/m ² (measured value under i-ray (wavelength: 365 nm)). After the exposure, after leaving at room temperature (23 ° C to 25 ° C) for 15 minutes, the support film 1 was removed, and then development was carried out by spraying a 1 mass% sodium carbonate aqueous solution at 30 ° C for 30 seconds. The conductive pattern of the photosensitive conductive film is formed on the resin hardened pattern by development. Next, the sensitivity is evaluated based on the number of remaining steps after development. The sensitivity of the photosensitive conductive film V1 was evaluated and found to be 8 steps. The higher the number of stages of the remaining ladder plates (the larger the value), the higher the sensitivity.

[Measurement of the resolution of the photosensitive conductive film V1 (full development process)] The photosensitive conductive film V1 was placed on the easy-contact surface of a PET film substrate (thickness: 50 μm, manufactured by Toyobo Co., Ltd., trade name "A4100"). The polyethylene film was peeled off, and a laminator (manufactured by Hitachi Chemical Co., Ltd., trade name "HLM-3000 type") was used in contact with the photosensitive resin layer, and the roll temperature was 110 ° C, and the substrate feed rate was Lamination was carried out under the conditions of 1 m/min and a pressure contact pressure (cylinder pressure) of 4 × 10 ⁵ Pa to prepare a film substrate on which a photosensitive conductive film V1 containing a support film was laminated on a PET film substrate.

Then, a PET mask having a wiring pattern having a line width/space width of 6/6 to 47/47 (unit: μm) is adhered to the support film 1 of the photosensitive conductive film on the film substrate, and parallel rays are used. The exposure machine (manufactured by ORC Manufacturing Co., Ltd., trade name "EXM1201") was exposed from the support film 1 side through a mask. The exposure amount was set to an exposure amount of 8 levels in the sensitivity of the 41-step ladder plate (manufactured by Hitachi Chemical Co., Ltd.). After the exposure, after leaving at room temperature (23 ° C to 25 ° C) for 15 minutes, the support film 1 was removed, and then development was carried out by spraying a 1 mass% sodium carbonate aqueous solution at 30 ° C for 30 seconds. By observing the developed conductive pattern by an optical microscope, it was confirmed that the conductive layer of the unexposed portion can be completely removed by the development treatment, and the exposed portion can form the conductive pattern without any defect. The resolution is evaluated based on the minimum value of the line width/space width. The result of evaluation of the resolution of the photosensitive conductive film V1 was 25 μm. The smaller the value, the better the evaluation of the resolution.

[Measurement of the resolution of the photosensitive conductive film V1 (low-order-difference development process)] Photosensitive conductive on the easy-contact surface of a PET film substrate (thickness: 50 μm, manufactured by Toyobo Co., Ltd., trade name "A4100") The polyethylene film of the film V1 was peeled off, and a laminator (manufactured by Hitachi Chemical Co., Ltd., trade name "HLM-3000 type") was used to contact the photosensitive resin layer, and the substrate temperature was 110 ° C. Lamination was carried out under the conditions of a speed of 1 m/min and a pressure contact pressure (cylinder pressure) of 4 × 10 ⁵ Pa, and a film substrate on which a photosensitive conductive film V1 containing a support film was laminated on a PET film substrate was produced.

Then, a PET mask having a wiring pattern having a line width/space width of 6/6 to 47/47 (unit: μm) is adhered to the support film 1 of the photosensitive conductive film on the film substrate, and parallel rays are used. The exposure machine (manufactured by ORC Co., Ltd., trade name "EXM1201") was exposed to the mask from the side of the support film 1 (first-stage exposure). The exposure amount was set to an exposure amount of 8 levels in the sensitivity of the 41-step ladder plate (manufactured by Hitachi Chemical Co., Ltd.). Then, the mask and the support film 1 are removed, and the entire surface of the film is exposed (second-stage exposure) in an atmosphere (in the presence of oxygen) from above the conductive layer of the photosensitive conductive film. The exposure amount is set to 3 times the exposure amount of the previous first stage exposure.

After the exposure, the mixture was allowed to stand at room temperature (23 ° C to 25 ° C) for 15 minutes, and then developed by spraying a 1 mass% sodium carbonate aqueous solution at 30 ° C for 30 seconds. By observing the developed conductive pattern by an optical microscope, it is confirmed that the conductive fiber of the conductive layer can be completely removed from the unexposed portion during the first-stage exposure by the development process, and can be in the first stage. At the time of exposure, the pattern of the conductive fiber was formed without any defect in the exposed portion, and the resolution was evaluated based on the minimum value of the line width/space width. The result of evaluation of the resolution of the photosensitive conductive film V1 was 20 μm. The smaller the value, the better the evaluation of the resolution.

Example 2 to Example 6 A photosensitive conductive film was produced in the same manner as in Example 1 except that the solution (X) of the photosensitive resin composition shown in Table 4 was used, and various characteristics were evaluated. The results are shown in Table 4.

[Example 7 and Example 8] A photosensitive conductive film was produced in the same manner as in Example 1 except that the conductive film W2 or the conductive film W3 was used instead of the conductive film W1, and various characteristics were evaluated. The results are shown in Table 4. The manufacturing method of the conductive film W2 and the conductive film W3 is as follows.

[Production of Conductive Film (Conductive Film of Photosensitive Conductive Film) W2] The silver fiber dispersion obtained in the above Production Example 1 was uniformly applied to a 50 μm thick poly(terephthalic acid) at 20 g/m ² The ethylene glycol film (PET film, manufactured by Teijin Co., Ltd., trade name "G2-50") was dried by a hot air convection dryer at 100 ° C for 3 minutes to form a conductive film W2. The film thickness after drying of the conductive film was 0.08 μm.

[Production of Conductive Film (Conductive Film of Photosensitive Conductive Film) W3] The carbon nanotube dispersion obtained in the above Production Example 1 was uniformly coated at 30 g/m ² on a polypyrylene having a thickness of 50 μm. The ethylene formate film (PET film, manufactured by Teijin Co., Ltd., trade name "G2-50") was dried by a hot air convection dryer at 100 ° C for 3 minutes to form a conductive film W3. The film thickness after drying of the conductive film was 0.05 μm.

Comparative Example 1 to Comparative Example 3 A photosensitive conductive film was produced in the same manner as in Example 1 except that the solution (X) of the photosensitive resin composition shown in Table 5 was used, and various characteristics were evaluated. The results are shown in Table 5.

Comparative Example 4 A photosensitive conductive film was produced in the same manner as in Example 1 except that the conductive film W3 was used instead of the conductive film W1, and a solution (X) of the photosensitive resin composition shown in Table 5 was used. Conduct an evaluation. The results are shown in Table 5.

[Table 4]

[table 5]

As shown in Tables 4 and 5, it was confirmed that the resolution was improved by using a photosensitive layer containing the ultraviolet absorber as the component (D). More specifically, it was confirmed that Examples 1 to 7 in which the photosensitive layer contains the silver nanowires showed superior resolution compared with Comparative Examples 1 to 3, and the photosensitive layer contained the carbon nanotubes. 8 showed superior resolution compared with Comparative Example 4. [Industrial availability]

When the photosensitive conductive film of the present invention is used, even when the photosensitive layer contains conductive fibers, the conductive pattern can be formed with sufficient resolution. In addition, it can be used for the production of a substrate with a conductive pattern having sufficient resolution, and for the manufacture of a touch panel comprising a substrate with a conductive pattern.

1‧‧‧Support film
2‧‧‧Electrical film
2a‧‧‧ conductive pattern
3‧‧‧Photosensitive resin layer
3a‧‧‧ resin hardened layer
3b‧‧‧Resin hardening pattern
4‧‧‧Photosensitive layer
5‧‧‧Protective film
6‧‧‧ mask pattern
10,12‧‧‧Photosensitive conductive film
20‧‧‧Substrate
40, 41, 42‧‧‧Substrate with conductive pattern
101‧‧‧Transparent substrate
102‧‧‧ touch screen
103‧‧‧Transparent Electrode (X Position Coordinate)
104‧‧‧Transparent Electrode (Y Position Coordinate)
Ha, Hb‧‧ ‧ step
L‧‧‧ actinic ray

Fig. 1 is a schematic cross-sectional view showing an embodiment of a photosensitive conductive film. Fig. 2 is a partially cutaway perspective view showing an embodiment of a photosensitive conductive film. 3(a), 3(b), and 3(c) are schematic cross-sectional views for explaining an embodiment of a method of forming a conductive pattern using a photosensitive conductive film. 4(a), 4(b) and 4(c) are schematic cross-sectional views for explaining another embodiment of a method of forming a conductive pattern using a photosensitive conductive film. 5(a), 5(b), 5(c), and 5(d) are schematic cross-sectional views for explaining another embodiment of a method of forming a conductive pattern using a photosensitive conductive film. 6 is a schematic plan view showing an example of a capacitive touch panel sensor.

1‧‧‧Support film

2‧‧‧Electrical film

3‧‧‧Photosensitive resin layer

4‧‧‧Photosensitive layer

5‧‧‧Protective film

10‧‧‧Photosensitive conductive film

Claims (9)

A photosensitive conductive film comprising: a support film, and a photosensitive layer disposed on the support film, and the photosensitive layer comprises: a conductive fiber, a binder polymer, a photopolymerizable compound, a photopolymerization initiator And UV absorbers. The photosensitive conductive film according to claim 1, wherein the ultraviolet absorber has a maximum absorption wavelength in a wavelength range of 250 nm or more and 400 nm or less. In the photosensitive conductive film according to the first or second aspect of the invention, the minimum value of the visible light transmittance in the wavelength range of 400 nm or more and 700 nm or less is 85% or more. The photosensitive conductive film according to any one of claims 1 to 3, wherein the ultraviolet absorber has a thermally polymerizable group or a photopolymerizable group. The photosensitive conductive film according to any one of claims 1 to 3, wherein the ultraviolet absorber is a polymer type ultraviolet absorber. The photosensitive conductive film according to any one of the items 1 to 5, wherein the conductive fiber is a silver fiber. A method of forming a conductive pattern, comprising: transferring a photosensitive layer of the photosensitive conductive film according to any one of claims 1 to 6 to a substrate; exposing step, turning The photosensitive layer printed on the substrate is irradiated with actinic rays in a pattern; and a developing step of forming a conductive pattern by removing unexposed portions of the photosensitive layer. A substrate with a conductive pattern comprising a substrate and a conductive pattern formed on the substrate by a method as described in claim 7 of the patent application. A touch panel sensor comprising the substrate with a conductive pattern as described in claim 8 of the patent application.