JPWO2016167228A1 - Photosensitive conductive film, method for forming conductive pattern, substrate with conductive pattern, and touch panel sensor - Google Patents

Abstract

A photosensitive film comprising 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; the film.

Description

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

  Liquid crystal display elements or touch panel sensors are used in large electronic devices such as personal computers and televisions, small electronic devices such as car navigation systems, mobile phones, and electronic dictionaries, and display devices such as OA devices and FA devices. These liquid crystal display elements and touch panel sensors require a transparent electrode material.

  Various types of touch panels have already been put into practical use. In recent years, the use of capacitive touch panels has progressed. In a capacitive touch panel, when a fingertip (conductor) contacts the touch input surface, the fingertip and the conductive film are capacitively coupled to form a capacitor. The capacitive touch panel detects the coordinates by capturing the change in charge at the contact position of the fingertip.

  In particular, a projected capacitive touch panel has a good operability such that a complex instruction can be performed because multiple fingertip detection is possible. Due to its good operability, a projected capacitive touch panel is increasingly used as an input device on a display surface in a device having a small display device such as a mobile phone and a portable music player.

  In general, in a projected capacitive touch panel, a plurality of X electrodes and a plurality of Y electrodes perpendicular to the X electrodes form a two-layer structure in order to express two-dimensional coordinates based on the X and Y axes. doing. A transparent electrode material is used for these electrodes.

  Conventionally, ITO, indium oxide, tin oxide, and the like have been used for transparent electrode materials because they exhibit high light transmittance. However, recently, attempts have been made to form a transparent electrode (transparent conductive pattern) using a material instead of these. For example, Patent Document 1 below proposes a method for forming a conductive pattern using a photosensitive conductive film having a photosensitive layer containing conductive fibers. If this technique is used, a conductive pattern can be easily formed directly on various substrates by a photolithography process.

International Patent Publication No. 2010/021224

  In the photosensitive conductive film described in Patent Document 1, it is possible to easily form conductive patterns on various substrates, but patterning is performed by exposing and developing a photosensitive layer containing conductive fibers. The present inventor has found that the resolution tends to decrease when performing.

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

  As a result of studying to solve the above-mentioned problems, the present inventor has found that the resolution can be improved by blending a photosensitive layer containing conductive fibers with an ultraviolet absorber, and the present invention has been completed.

  The present invention comprises a support film and a photosensitive layer provided on the support film, the photosensitive layer comprising conductive fibers, a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and an ultraviolet absorber. A photosensitive conductive film is provided.

  According to the photosensitive conductive film of the present invention, a conductive pattern containing conductive fibers can be formed with sufficient resolution. This is presumably because the photosensitive layer has the above composition containing an ultraviolet absorber, so that the scattered light generated by the conductive fibers is absorbed during patterning, and the influence of halation can be reduced.

  The ultraviolet absorber may have a maximum absorption wavelength in a wavelength range of 250 nm to 400 nm. Such an ultraviolet absorber can effectively absorb the scattered light from the conductive fiber, and can further suppress a reduction in resolution to a higher degree.

  The photosensitive conductive film may have a minimum visible light transmittance of 85% or more at 400 to 700 nm. When the minimum value of the visible light transmittance is in the above range, it is possible to provide a conductive pattern which is not colored and has excellent transparency.

  The ultraviolet absorber may have a thermally polymerizable group or a photopolymerizable group. When such an ultraviolet absorber is used, the bleeding of the ultraviolet absorber from the photosensitive layer or a cured product thereof can be further suppressed.

  The ultraviolet absorber may be a polymer type ultraviolet absorber. When such an ultraviolet absorber is used, the bleeding of the ultraviolet absorber from the photosensitive layer or a cured product thereof can be further suppressed.

  The conductive fiber may be a silver fiber. By using silver fiber, a photosensitive conductive film having high visible light transmittance in the wavelength region of 400 nm to 700 nm and high conductivity can be provided.

  The present invention also includes a step of transferring the photosensitive layer of the photosensitive conductive film of the present invention onto a substrate, an exposure step of irradiating the photosensitive layer transferred onto the substrate with actinic rays in a pattern, and the above And a development step of forming a conductive pattern by removing an unexposed portion of the photosensitive layer.

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

  This invention also provides the base material with a conductive pattern which has a base material and the conductive pattern formed by the formation method of the conductive pattern of this invention on the said base material.

  Since the substrate with a conductive pattern of the present invention has a conductive pattern formed by the above-described method for forming a conductive pattern, a conductive pattern with excellent resolution, that is, a thinner conductive pattern and a thinner space portion (photosensitive layer removal) Part).

  Moreover, this invention provides a touchscreen sensor provided with the base material with a conductive pattern of this invention.

  Since the touch panel sensor of the present invention includes the above-described base material with a conductive pattern, the pattern appearance of the conductive pattern can be reduced, and the visibility can be improved (the pattern is difficult to see).

  According to the present invention, a photosensitive conductive film capable of forming a conductive pattern containing conductive fibers with sufficient resolution, a method for forming a conductive pattern, a substrate with a conductive pattern having a conductive pattern with excellent resolution, and A touch panel can be provided.

It is a schematic cross section showing one embodiment of a photosensitive conductive film. It is a partially cutaway perspective view showing one embodiment of a photosensitive conductive film. It is a schematic cross section for demonstrating one Embodiment of the formation method of the conductive pattern using the photosensitive conductive film. It is a schematic cross section for demonstrating another embodiment of the formation method of the conductive pattern using the photosensitive conductive film. It is a schematic cross section for demonstrating another embodiment of the formation method of the conductive pattern using the photosensitive conductive film. It is a model top view which shows an example of an electrostatic capacitance type touch panel sensor.

Hereinafter, preferred embodiments of the present invention will be described in detail. The “(meth) acrylate” in the present specification means “acrylate” or “methacrylate”. Similarly, “(meth) acrylic acid” means “acrylic acid” or “methacrylic acid”, and “(meth) acryloyl group” means “acryloyl group” or “methacryloyl group”. Moreover, the numerical range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively.
“A or B” only needs to include one of A and B, or may include both. In addition, the exemplary materials may be used alone or in combination of two or more unless otherwise specified.

<Photosensitive conductive film>
The photosensitive conductive film according to the present embodiment includes a support film and a photosensitive layer provided on the support film, and the photosensitive layer includes conductive fibers, a binder polymer, a photopolymerizable compound, and a photopolymerization initiator. , And an ultraviolet absorber. One embodiment of the photosensitive conductive film is shown in FIG. 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. In addition, since the photosensitive conductive film is used to transfer the photosensitive layer onto the base material and form the photosensitive layer on the base material, it can also be said to be a transfer type photosensitive conductive film.

  In FIG. 1, the photosensitive conductive film 10 is illustrated so that the boundary between the conductive film 2 and the photosensitive resin layer 3 provided on the conductive film 2 is clear. The boundary with the conductive resin layer 3 is not necessarily clear. Any conductive film may be used as long as conductivity is obtained in the surface direction of the photosensitive layer, and the conductive resin may be mixed with the photosensitive resin layer. For example, the composition constituting the photosensitive resin layer may be impregnated in the conductive film, or the composition constituting the photosensitive resin layer may be present on the surface of the conductive film.

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

  Examples of the support film 1 include 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 preferable from the viewpoint of transparency and heat resistance. These polymer films may be surface-treated so as to be easily peeled off from the photosensitive layer 4, and are preferably materials that can be easily peeled off from the photosensitive layer 4.

  The thickness of the support film 1 is preferably 5 to 300 μm, more preferably 10 to 200 μm, still more preferably 15 to 100 μm, and particularly preferably 30 to 70 μm. A step of applying a photosensitive resin composition to form a conductive dispersion or a photosensitive resin layer 3 to form the conductive film 2, or a support film before developing the exposed photosensitive resin layer 3 In the step of peeling, from the viewpoint of preventing mechanical strength from being reduced and the support film from being broken, it is preferably 5 μm or more, more preferably 10 μm or more, further preferably 15 μm or more, and 30 μm. The above is particularly preferable. In addition, from the viewpoint of better pattern resolution when the photosensitive resin layer is irradiated with actinic rays through the support film, it is preferably 300 μm or less, more preferably 200 μm or less, and 100 μm or less. More preferably, it is particularly preferably 70 μm or less.

  The haze value of the support film 1 is preferably 0.01 to 5.0%, more preferably 0.01 to 3.0%, from the viewpoint of improving sensitivity and resolution. More preferably, it is -2.0%, and it is especially preferable that it is 0.01-1.0%. The haze value can be measured according to JIS K 7375 (established in 2008). It can also be measured with a commercially available turbidimeter such as NDH-1001DP (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.).

  Examples of the conductive fiber include metal fibers such as gold, silver, copper, and platinum, or carbon fibers such as carbon nanotubes. From the point that the method for preparing the conductive fiber is simple, the shape of the conductive fiber is easy to control, high visible light transmittance in the wavelength range of 400 to 700 nm, and high conductivity. As the conductive fiber, silver fiber is preferable, and silver nanowire is more preferable. Here, the nanowire is, for example, a small difference in size between two dimensions (X, Y) (specifically, the difference in size is 5 times or less), and both X and Y are 300 nm or less. This is a size, and indicates a shape in which the size of one remaining dimension (Z) is 10 times or more of X and Y.

  FIG. 2 is a partially cutaway perspective view showing an embodiment of a photosensitive conductive film. The conductive film 2 preferably has a network structure in which conductive fibers are in contact with each other like the photosensitive conductive film 12 shown in FIG. The conductive film 2 having such a network structure may be formed on the surface of the photosensitive resin layer 3 on the support film 1 side, but on the surface of the photosensitive layer 4 exposed when the support film 1 is peeled off. As long as conductivity is obtained in the surface direction, the conductive film 2 may be formed so that a part of the photosensitive resin layer 3 enters the conductive film 2, and the conductive film is formed on the surface layer of the photosensitive resin layer 3 on the support film 1 side. 2 may be included.

The conductive fibers including silver fibers or silver nanowires can be prepared by, for example, 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 1 nm to 100 nm, more preferably 2 nm to 50 nm, and further preferably 3 nm to 30 nm. The fiber length of the conductive fiber is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm, and further preferably 3 μm to 10 μm. The fiber diameter and fiber length can be measured with a scanning electron microscope.

  An organic conductor may be used for the conductive film 2 together with the conductive fiber. The organic conductor can be used without particular limitation, but from the viewpoint of high transparency and conductivity, it is preferable to use an organic conductor such as a polymer of a thiophene derivative and an aniline derivative. Specifically, polyethylenedioxythiophene, polyhexylthiophene, polyaniline, polyvinylpyrrolidone, or the like can be used.

  The thickness of the conductive film 2 varies depending on the use of the conductive pattern formed using the photosensitive conductive film of the present invention and the required conductivity, but is preferably 1 μm or less, and preferably 1 nm to 0.5 μm. Is more 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 region of 400 to 700 nm is high, the pattern formation is excellent, and it is particularly suitable for the production of a transparent electrode. The thickness of the conductive film 2 indicates a value measured by a scanning electron microscope.

  For example, after the conductive film 2 is coated on the support film 1 with a conductive dispersion obtained by adding the above-described conductive fiber or organic conductor to water or an organic solvent, a dispersion stabilizer such as a surfactant, and the like, It can be formed by drying. After drying, the conductive film 2 formed on the support film 1 may be laminated as necessary.

  The coating can be performed 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. The drying can be performed at 30 to 150 ° C. for about 1 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 conductive fibers. The greater the amount of conductive fiber, the lower the surface resistivity of the conductive film, and the higher the conductivity. On the other hand, the greater the amount of conductive fiber, the lower the transmittance. Further, as the amount of the conductive fiber increases, the light scattering by the conductive fiber becomes stronger, and the resolution tends to decrease.

  In the present embodiment, the photosensitive layer only needs to contain an ultraviolet absorber. For example, the conductive film is formed using a conductive dispersion containing the ultraviolet absorber, and the ultraviolet absorber is present in the conductive film. Alternatively, an ultraviolet absorber may be present in the photosensitive resin layer. For example, a conductive film formed by coating a conductive dispersion containing an ultraviolet absorber on a support film and drying, or a photosensitive conductive film formed by forming a photosensitive resin layer on the conductive film In addition, an ultraviolet absorber can be contained.

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

  (A) As binder polymer, epoxy resin obtained by reaction of acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, epoxy resin and (meth) acrylic acid Examples thereof include acid-modified epoxy acrylate resins obtained by reaction of acrylate resins and epoxy acrylate resins with acid anhydrides.

  Among these, from the viewpoint of excellent alkali developability and film formability, it is preferable to use an acrylic resin, and the acrylic resin is derived from (meth) acrylic acid and a (meth) acrylic acid alkyl ester as a constituent unit. More preferably. Here, “acrylic resin” means a polymer mainly having a monomer unit derived from a polymerizable monomer having a (meth) acryloyl group.

  As the acrylic resin, one produced by radical polymerization of a polymerizable monomer having a (meth) acryloyl group can be used.

  Examples of the polymerizable monomer having a (meth) acryloyl group include acrylamide such as diacetone acrylamide; (meth) acrylic acid alkyl ester, 2-hydroxyalkyl (meth) acrylate, (meth) acrylic acid tetrahydrofurfuryl ester, ( (Meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2, (Meth) acrylic acid esters such as 2,3,3-tetrafluoropropyl (meth) acrylate; (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl ( (Meth) acrylic acid, β-styryl (meth) (Meth) acrylic acid such as acrylic acid.

  In addition to the polymerizable monomer having the (meth) acryloyl group as described above, the acrylic resin includes styrene derivatives; acrylonitrile; esters of vinyl alcohol such as vinyl-n-butyl ether; maleic acid; maleic anhydride; By copolymerizing monomeric monomers such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate; fumaric acid; cinnamic acid; α-cyanocinnamic acid; itaconic acid; crotonic acid and the like. It may be manufactured.

  As the (meth) acrylic acid alkyl ester, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid hexyl ester, Examples include (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, and the like.

  (A) It is preferable that a binder polymer has a carboxyl group from a viewpoint of making alkali developability more favorable. Examples of the polymerizable monomer having a carboxyl group include (meth) acrylic acid as described above.

  (A) The ratio of the carboxyl group that the binder polymer has is preferably 10 to 50% by mass, and preferably 12 to 40% by mass, as the ratio of the polymerizable monomer having a carboxyl group to the total polymerizable monomer to be used. It is more preferable that it is 12-30 mass%, and it is especially preferable that it is 12-25 mass%. In terms of excellent alkali developability, the content is preferably 10% by mass or more, and in terms of excellent alkali resistance, it is preferably 50% by mass or less. (A) The binder polymer is preferably a binder polymer having a structural unit based on (meth) acrylic acid and a structural unit based on (meth) acrylic acid methyl ester or a structural unit based on (meth) acrylic acid ethyl ester. Binder polymers having a structural unit based on (meth) acrylic acid, a structural unit based on (meth) acrylic acid methyl ester, and a structural unit based on (meth) acrylic acid ethyl ester are more preferred.

  (A) The weight average molecular weight of the binder polymer is preferably 5,000 to 300,000, more preferably 20,000 to 150,000, and more preferably 30,000 to 100,000 from the viewpoint of balancing the mechanical strength and alkali developability. Further preferred. In terms of excellent developer resistance, the weight average molecular weight is preferably 5000 or more. Further, from the viewpoint of development time, it is preferably 300000 or less. In this specification, the weight average molecular weight is a value measured by a gel permeation chromatography method (GPC) and converted by a calibration curve created using standard polystyrene.

  (A) The acid value of the binder polymer is preferably 75 to 200 mgKOH / g, more preferably 75 to 150 mgKOH / g, and 75 to 120 mgKOH / g from the viewpoint of excellent pattern forming properties. More preferably, it is especially preferable that it is 78-120 mgKOH / g.

(A) The acid value of a binder polymer can be measured as follows. First, 1 g of the binder polymer that is the object of acid value measurement is precisely weighed. 30 g of acetone is added to the precisely weighed binder polymer and dissolved uniformly. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N aqueous KOH solution. And an acid value is computed by following Formula.
Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100)
In the formula, Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the weight (g) of the solution containing the measured binder polymer, and I represents the ratio of the nonvolatile content in the solution containing the measured binder polymer ( Mass%).
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 is heated in advance for 1 to 4 hours at a temperature higher than the boiling point of the volatile component by 1 to 4 hours before precise weighing. The acid value may be measured after removing.

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

  Examples of the photopolymerizable compound having an ethylenically unsaturated bond include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypoly). Bisphenol A di (meth) acrylate compounds such as propoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane; polyethylene glycol di (meth) acrylate, polypropylene glycol di Polyalkylene glycol di (meth) acrylates such as (meth) acrylate and polyethylene polypropylene glycol di (meth) acrylate; trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxy Trimethylolpropane (meth) acrylates such as li (meth) acrylate and trimethylolpropane triethoxytri (meth) acrylate; tetramethylolmethane such as tetramethylolmethane tri (meth) acrylate and tetramethylolmethanetetra (meth) acrylate (meta ) Acrylates; dipentaerythritol (meth) acrylates such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, urethane monomers, and the like.

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

  (B) The content ratio of the photopolymerizable compound is preferably 30 to 80% by mass, more preferably 40 to 70% by mass with respect to 100% by mass of the total of the binder polymer and the photopolymerizable compound. . It is preferably 30% by mass or more in terms of excellent coating properties of the photocurable and photosensitive resin composition, and 80% by mass or less in terms of excellent storage stability when wound as a film. Is preferred.

  (C) The photopolymerization initiator will be described. The photopolymerization initiator is not particularly limited as long as the photopolymerization initiator is selected so that the light wavelength of the exposure machine to be used matches the wavelength necessary for function expression. Examples of the photopolymerization initiator include benzophenone, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N, N ′, N′-tetraethyl-4,4. '-Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) Aromatic ketones such as phenyl] -2-morpholino-propanone-1; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; 1,2-octane Dione-1- [4- (phenylthio) phenyl]- Oxime ester compounds such as-(O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); Benzyl derivatives such as benzyl dimethyl ketal; phosphine oxide compounds, oxazole compounds and the like.

  Among these, an oxime ester compound or a phosphine oxide compound is preferable as the photopolymerization initiator because of transparency and pattern forming ability when the photosensitive layer is a thin film (for example, 10 μm or less).

上記一般式（Ｃ−１）中、Ｒ^１は、炭素数１〜１２のアルキル基、又は炭素数３〜２０のシクロアルキル基を示す。Ｒ^１は、炭素数３〜９のアルキル基が好ましい。なお、本発明の効果を阻害しない限り、上記一般式（Ｃ−１）中の芳香環に置換基を有していてもよい。置換基としては、水素原子又は炭素数１〜１２のアルキル基が挙げられる。Examples of the oxime ester compound include compounds represented by the following general formula (C-1) and general formula (C-2). From the viewpoint of fast curability and transparency, a compound represented by the following general formula (C-1) is preferred.

In the general 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. In addition, as long as the effect of this invention is not inhibited, you may have a substituent in the aromatic ring in the said general formula (C-1). Examples of the substituent include a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

上記一般式（Ｃ−２）中、Ｒ^２は水素原子又は炭素数１〜１２のアルキル基を示し、Ｒ^３は、炭素数１〜１２のアルキル基、又は炭素数３〜２０のシクロアルキル基を示し、Ｒ^４は、炭素数１〜１２のアルキル基を示し、Ｒ^５は、炭素数１〜２０のアルキル基又はアリール基を示す。ｐ１は０〜３の整数を示す。ｐ１が２以上である場合、複数のＲ^４はそれぞれ同一でも異なっていてもよい。また、カルバゾール構造には本発明の効果を阻害しない範囲で置換基を有していてもよい。置換基としては、水素原子又は炭素数１〜１２のアルキル基が挙げられる。

In the general formula ^{(C-2), R} 2 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, ^{R 3} is an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms R ⁴ represents an alkyl group having 1 to 12 carbon atoms, and R ⁵ represents an alkyl group or aryl group having 1 to 20 carbon atoms. p1 represents an integer of 0 to 3. When p1 is 2 or more, the plurality of R ⁴ may be the same or different. Further, the carbazole structure may have a substituent as long as the effects of the present invention are not impaired. Examples of the substituent include a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

In the general 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, and 1 to 4 carbon atoms. More preferably, it is an alkyl group.

In the general 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, and an alkyl group having 1 to 4 carbon atoms or a carbon number. It is more preferably a 4-10 cycloalkyl group, and particularly preferably a methyl group or an ethyl group.

In general 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, and an alkyl group having 1 to 8 carbon atoms or 6 to 14 carbon atoms. Is more preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

  Examples of the compound represented by the general formula (C-1) include 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), and IRGACURE OXE. It is commercially available as 01 (BASF Corporation, trade name). Examples of the compound represented by the general formula (C-2) include ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl). Oxime) and the like, and is commercially available as IRGACURE OXE 02 (trade name, manufactured by BASF Corporation).

  As a phosphine oxide compound, the compound represented by the following general formula (C-3) and general formula (C-4) is mentioned. From the viewpoint of fast curability and transparency, a compound represented by the following general formula (C-3) is preferred.

In said general formula (C-3), R < ⁶ >, R < ⁷ > and R < ⁸ > show a C1-C20 alkyl group or aryl group each independently. In general formula (C-4), R <^9> , R < ¹⁰ > and R < ¹¹ > show a C1-C20 alkyl group or an aryl group each independently.

When R ⁶ , R ⁷ or R ⁸ in the general formula (C-3) is an alkyl group having 1 to 20 carbon atoms, and R ⁹ , R ¹⁰ or R ¹¹ in the general formula (C-4) are In the case of 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. .

When R ⁶ , R ⁷ or R ⁸ in the general formula (C-3) is an aryl group, and when R ⁹ , R ¹⁰ or R ¹¹ in the general formula (C-4) is an aryl group, the aryl The 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, in the general formula (C-3), R ⁶ , R ⁷ , and R ⁸ are preferably aryl groups. In the general formula (C-4), R ⁹ , R ¹⁰ and R ¹¹ are preferably aryl groups.

  As the compound represented by the general formula (C-3), 2,4,6-trimethyl is obtained from the transparency of the formed conductive pattern and the pattern forming ability when the film thickness is reduced (for example, 10 μm or less). Benzoyl-diphenyl-phosphine oxide is preferred. 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide is commercially available, for example, as LUCIRIN TPO (trade name, manufactured by BASF Corporation).

  As the compound represented by the general formula (C-4), bis (2, 4, 6) is obtained from the transparency of the conductive pattern to be formed and the pattern forming ability when the film thickness is reduced (for example, 10 μm or less). -Trimethylbenzoyl) -phenyl-phosphine oxide is preferred. Bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide is commercially available, for example, as Irgacure 819 (trade name, manufactured by BASF Corporation).

  Other than oxime ester compounds and phosphine oxide compounds, 2,2-dimethoxy-1,2-diphenylethane-1-one may be used as a compound having good transparency and pattern forming ability when the photosensitive layer is thinned. Is preferred. 2,2-dimethoxy-1,2-diphenylethane-1-one is commercially available, for example, as Irgacure 651 (trade name, manufactured by BASF Corporation).

  (C) The photopolymerization initiator is 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl It is particularly preferable to use either -phosphine oxide or 2,2-dimethoxy-1,2-diphenylethane-1-one.

  The content ratio of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass in total of the binder polymer and the photopolymerizable compound. More preferably, it is 1-5 mass parts. In terms of excellent photosensitivity, it is preferably 0.1 parts by mass or more, and in terms of excellent photocurability, it is preferably 20 parts by mass or less.

  (D) The ultraviolet absorber will be described. (D) The ultraviolet absorber is excellent in the ability to absorb ultraviolet light having a wavelength of 400 nm or less from the viewpoint of scattered light absorption by the conductive fiber, and has little absorption of visible light having a wavelength of 400 nm or more from the viewpoint of improving transparency. Those are preferred. Specifically, a material having a maximum absorption wavelength in a wavelength range of 250 nm to 400 nm corresponds to this.

  (D) By containing the ultraviolet absorber in the photosensitive layer, it is possible to absorb the scattered light from the conductive fibers, suppress halation, and sufficiently suppress the decrease in resolution. 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, etc.), and the conductive fiber is corroded or deteriorated, thereby reducing the resistance of the conductive pattern. Although it may increase, an increase in resistance can be suppressed by including an ultraviolet absorber in the photosensitive layer.

  (D) Examples of the ultraviolet absorber include oxybenzophenone compounds, triazole compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, diphenyl acrylate compounds, cyanoacrylate compounds, diphenyl cyanoacrylate compounds, nickel complex salts, and the like. Among these, 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. Increasing the content of the ultraviolet absorber can be expected to improve the effect of the present invention. However, when the content of the ultraviolet absorber is increased, the ultraviolet absorber oozes from the cured resin after patterning. (Bleed out). Bleed-out of the ultraviolet absorber is not preferable because it may cause a decrease in transparency of the cured resin and deterioration of optical properties such as turbidity. Moreover, when content of a ultraviolet absorber increases, the ultraviolet absorber which is not taken in in resin cured | curing material may adsorb | suck to the surface of an electroconductive fiber. Adsorption of the ultraviolet absorbent to the conductive fiber is not preferable because it causes an increase in the resistance value of the conductive film. On the other hand, when the ultraviolet absorber has a reactive group, the ultraviolet absorber is fixed to the cured resin during patterning (for example, it is firmly connected and incorporated into the network of the cured resin by a covalent bond). Therefore, the ultraviolet absorber bleeds out (bleed out) or the movement of the ultraviolet absorber in the cured resin is suppressed. Therefore, even if the content of the ultraviolet absorber is increased, an increase in the resistance value due to the adsorption of the ultraviolet absorber to the conductive fiber surface can be suppressed.

  Examples of the thermally polymerizable group include an epoxy group, a glycidyl group, an isocyanate group, an acetylene group, a maleimide group, and an oxetanyl group. Examples of the photopolymerizable group include a (meth) acryloyl group, an allyl group, and a maleimide group. The thermopolymerizable group and the photopolymerizable group are not limited to the above examples. In the present embodiment, any ultraviolet absorber having a reactive group that can be polymerized by an active radical, an acid, or a base generated by heat or light can be used without particular limitation. Bleed out or adsorption to the surface of conductive fibers can be suppressed.

  Among the compounds having a thermally polymerizable group or a photopolymerizable group, it has a (meth) acryloyl group which is a photopolymerizable group from the viewpoint of availability and stability in the photosensitive conductive film before curing. Compounds are particularly preferred. Examples of such an ultraviolet absorber include 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole, which is a benzotriazole compound having a (meth) acryloyl group. . 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole is, for example, RUVA-93 (trade name, manufactured by Otsuka Chemical Co., Ltd.) or DAINSORB T-31 (Yamato (Trade name, manufactured by Kasei Co., Ltd.).

  (D) It is preferable that an ultraviolet absorber is a polymer type ultraviolet absorber. The polymer type ultraviolet absorber is an ultraviolet absorber obtained by polymerizing the compound having the above-mentioned heat-reactive group or photopolymerizable group. A polymer type ultraviolet absorber is a material having one or more ultraviolet absorption sites in a molecule and a large molecular weight. In the present specification, an ultraviolet absorber having a weight average molecular weight of 3000 or more is referred to as a polymer-type ultraviolet absorber. The polymer type ultraviolet absorber is one in which bleeding out is suppressed as compared with a low molecular weight ultraviolet absorber. In addition, the polymer-type ultraviolet absorber is hardly suppressed from being adsorbed on the surface of the conductive fiber. Thereby, it becomes possible to contain many ultraviolet absorbers in the photosensitive conductive film, and the influence of the scattered light by the conductive fibers can be reduced more effectively.

  As a polymer type ultraviolet absorber, photopolymerizability from the point of availability of a compound having a polymerizable reactive group as a raw material, easy adjustment of molecular weight, and wide selection of copolymerization components of the polymer A polymer polymerized using a compound having a (meth) acryloyl group as a raw material is preferred.

  Examples of the polymer type ultraviolet absorber include solvent-based RSA series (for example, RSA-0124, RSA-0151, and RSA-0191H; all manufactured by Sannan Synthetic Chemical Co., Ltd.), solvent-based PUVA series (for example, PUVA-30M- 50BA, PUVA-30M-30T, and PUVA-50M-50K; all manufactured by Daiwa Kasei Co., Ltd.), solvent-based RSU series (for example, RSU-0017 and SG-864; all manufactured by Daiwa Kasei Co., Ltd.) Water-based RWU series (for example, MW-022, RWU-0001, and RWU-0109; all manufactured by Daiwa Kasei Co., Ltd.) are commercially available. Also, aqueous New Coat UVA series (for example, New Coat UVA-101, New Coat UVA-102, New Coat UVA-103, and New Coat UVA-104), Solvent-based Vana Resin UVA series (for example, Vana Resin UVA-5080, hydroxyl group) Introducing vanaresin UVA-5080 (OHV20), vanaresin UVA-55T, high hydroxyl value type vanaresin UVA-55MHB, vanaresin UVA-7075, hydroxylintroducing vanaresin UVA-7075 (OHV20), vanaresin UVA-73T) and the like are new It is commercially available from Nakamura Chemical Co., Ltd. Solvent-based UVA series (for example, UVA-935LH and UVA-1935LH) and aqueous-based UVA series (for example, UVA-700 and UVA-1700) are commercially available from BASF Corporation.

  The weight average molecular weight of the polymer type ultraviolet absorber is preferably 300,000 or less, more preferably 150,000 or less, and more preferably 100,000 or less from the viewpoint of solubility in a solvent and compatibility with a photosensitive resin composition. More preferably it is. Further, from the viewpoint of preventing bleeding out from the photosensitive conductive film and its cured film, it is preferably 3000 or more, more preferably 5000 or more, and further preferably 10,000 or more. From the viewpoint of balancing the solubility in the solvent, the compatibility with the photosensitive resin composition, and the bleed-out prevention property, it is preferably 3,000 to 300,000, more preferably 5,000 to 150,000, and more preferably 10,000 to 100,000. More preferably. The weight average molecular weight is a value measured by a gel permeation chromatography method (GPC) and converted by a calibration curve prepared using standard polystyrene.

  (D) It is preferable that the content rate of a ultraviolet absorber is 0.1-30 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and is 1-20 mass parts. It is more preferable that the content is 2 to 10 parts by mass.

  (D) It is preferable that content of a ultraviolet absorber is 0.1 mass part or more in the point which suppresses the light scattering by an electroconductive fiber effectively, and is excellent in the resolution. Moreover, the point which prevents the bleed-out from the photosensitive conductive film and its cured film of an ultraviolet absorber, the point which suppresses adsorption | suction to the surface of a conductive fiber, or absorption on the surface of a photosensitive layer in the case of actinic ray irradiation Is preferably 30 parts by mass or less from the viewpoint of suppressing an increase in the amount of photocuring and insufficient internal photocuring.

  (D) As a method of incorporating the ultraviolet absorber into the photosensitive layer, a method of internally adding in advance to the photosensitive resin composition is common, but the present invention is not limited to the internal addition. Other methods for incorporating an ultraviolet absorber in the photosensitive layer include, for example, a method of internally adding an ultraviolet absorber in a conductive fiber dispersion, and a film containing conductive fibers formed on a support film that absorbs ultraviolet rays. There is a method of forming a conductive film by drying again after exposure to a liquid containing an agent. In order to contain a sufficient amount of UV absorber uniformly in the photosensitive resin composition and effectively suppress deterioration or disconnection of the conductive fiber due to UV rays, internal addition to the photosensitive resin composition in advance The method is most preferred.

  In the photosensitive resin composition of the present embodiment, if necessary, an adhesion imparting agent such as a silane coupling agent, a leveling agent, a plasticizer, a filler, an antifoaming agent, a flame retardant, a stabilizer, and an antioxidant. , Fragrance, thermal crosslinking agent, polymerization inhibitor and the like can be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B).

  The photosensitive resin layer 3 is a photosensitive resin composition dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. This solution can be formed by coating and drying on the support film 1 on which the conductive film 2 is formed. However, in this case, the amount of the remaining organic solvent in the photosensitive resin layer after drying is preferably 2% by mass or less in order to prevent the organic solvent from diffusing in the subsequent step.

  The photosensitive resin layer 3 can be applied 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. After coating, drying for removing the organic solvent and the like can be performed at 70 to 150 ° C. for about 5 to 30 minutes with a hot air convection dryer or the like.

  Although the thickness of the photosensitive resin layer 3 changes with uses, it is preferable that it is 1-50 micrometers in thickness after drying, it is more preferable that it is 1-15 micrometers, and it is further more preferable that it is 1-10 micrometers. If the thickness is less than 1 μm, coating tends to be difficult, and if it exceeds 50 μm, the sensitivity due to the decrease in light transmission is insufficient, and the photocuring property of the photosensitive resin layer to be transferred tends to decrease. The thickness of the layer (cured film) after curing the photosensitive resin layer 3 is also preferably within these ranges.

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

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

  In the photosensitive conductive film used in this embodiment, the protective film 5 may be laminated so as to be in contact with the surface of the photosensitive resin layer 3 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, and a polyethylene film can be used. Further, as the protective film 5, a polymer film similar to the above-described support film may be used.

The adhesive force between the protective film 5 and the photosensitive layer 4 is such that when the protective film is peeled off and laminated on the substrate from the photosensitive resin layer 3 side, the photosensitive layer is formed in order to make the protective film easy to peel off from the photosensitive layer. It is preferable that it is smaller than the adhesive force between 4 and the support film 1.
On the other hand, the adhesive force between the protective film 5 and the photosensitive layer 4 is such that when the support film 1 is peeled off and laminated to the base material from the conductive film 2 side, It is preferable that it is larger than the adhesive force between the layer 4 and the support film 1.

As for the protective film 5, it is preferable that the number of fish eyes with a diameter of 80 micrometers or more contained in a protective film is 5 pieces / m < ² > or less. “Fisheye” means that materials are melted, kneaded, extruded, biaxially stretched, casting materials, etc., and foreign materials, undissolved materials, oxidized degradation products, etc. are taken into the film. It is a thing.

  The thickness of the protective film 5 is preferably 1 to 100 μm, more preferably 5 to 50 μm, further preferably 5 to 30 μm, and particularly preferably 15 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 be lowered.

<Method for forming conductive pattern and substrate with conductive pattern>
The method for forming a conductive pattern of the present invention comprises a step of transferring the photosensitive layer of the photosensitive conductive film of the present invention onto a substrate (also referred to as a laminating step), and a pattern active on the photosensitive layer transferred onto the substrate. An exposure step of irradiating light and a development step of forming a conductive pattern by removing an unexposed portion of the photosensitive layer. Hereinafter, a method for forming a conductive pattern of the present invention will be described with reference to the drawings.

  FIG. 3 is a schematic cross-sectional view for explaining one embodiment of a conductive pattern forming method using a photosensitive conductive film. A method for forming a conductive pattern according to the present embodiment includes a laminating process in which the above-described photosensitive conductive film 10 is laminated so that the support film 1 is peeled off and the conductive layer 2 is in close contact with the base material 20 (FIG. 3A And a patterning step of forming a conductive pattern by exposing and developing the photosensitive layer 4 on the substrate (FIGS. 3B and 3C). The patterning step includes an exposure step (FIG. 3B) in which a predetermined portion of the photosensitive layer 4 having the protective film 5 is irradiated with an actinic ray, and then a developing step (developing the photosensitive layer 4 by peeling off the protective film 5). FIG. 3 (c)). Thus, the base material 40 with a conductive pattern is obtained.

  FIG. 4 is a schematic cross-sectional view for explaining another embodiment of a conductive pattern forming method using a photosensitive conductive film. The conductive pattern forming method according to the present embodiment is different from the conductive pattern forming method described above in that the photosensitive resin layer 3 is laminated so as to be in close contact with the substrate 20 when the photosensitive layer is laminated. That is, a photosensitive conductive film 10 having a support film 1, a conductive film 2, and a photosensitive resin layer 3 is prepared, and the photosensitive resin layer 3 of the photosensitive conductive film 10 is in close contact with the base material 20. A photosensitive layer is laminated on 20 (FIG. 4A). Next, the photosensitive resin layer 3 is irradiated with an actinic ray L in a pattern via the mask pattern 6 (FIG. 4B), the support film 1 is peeled off, and an uncured portion (unexposed portion) is developed by development. ) Is removed to form a conductive pattern 2a (FIG. 4C).

  The conductive pattern forming method includes the steps of laminating the photosensitive conductive film of the present invention so that the photosensitive resin layer is in close contact with the substrate, and the photosensitive resin layer on the substrate with the support film attached. An exposure step of irradiating the predetermined portion with actinic rays, a step of peeling off the support film, and a development step of forming a conductive pattern by developing the exposed photosensitive resin layer. By passing through these processes, the base material 41 with a conductive pattern provided with the conductive pattern patterned on the base material is obtained. The conductive pattern thus obtained has the thickness of the resin cured pattern 3b in addition to the thickness of the conductive pattern 2a. These thicknesses form a step Hb with the base material, and if this step is large, it becomes difficult to obtain the smoothness required for a display or the like. Further, when the step is large, the conductive pattern is easily visually recognized. Therefore, the method shown in FIG.

  FIG. 5 is a schematic cross-sectional view for explaining another embodiment of a method for forming a conductive pattern using a photosensitive conductive film. After the first exposure step (FIG. 5B) for irradiating a predetermined portion of the photosensitive layer 4 having the support film 1 with an actinic ray, the first exposure step is performed in the presence of oxygen after the support film 1 is peeled off. And a second exposure step (FIG. 5C) for irradiating a part or all of the exposed portion and the unexposed portion with actinic rays. The second exposure step is preferably performed in the presence of oxygen, for example, in air. Moreover, the conditions which increased oxygen concentration may be sufficient.

  In the developing step of the conductive pattern forming method of FIG. 5, the surface portion of the photosensitive resin layer 3 exposed in the second exposure step that has not been sufficiently cured is removed. Specifically, the surface portion of the photosensitive resin layer 3 that is not sufficiently cured, that is, the surface layer including the conductive film 2 is removed by the wet phenomenon. Thereby, the resin cured layer which does not have a conductive film with a conductive pattern is provided on the base material 20, the base material 42 with a conductive pattern is obtained, and it is conductive compared with the case where only a conductive pattern is provided on the base material. The level difference Ha of the pattern can be reduced.

  The conductive pattern forming method includes a step of laminating the photosensitive conductive film of the present invention so that the photosensitive resin composition is in close contact with the substrate, a photosensitive resin layer provided on the substrate, A first exposure step of irradiating a photosensitive layer including a conductive film provided on a surface of the photosensitive resin layer opposite to the substrate with an actinic ray in a pattern; and in the presence of oxygen, the photosensitive layer A second exposure step of irradiating a part or all of the unexposed portion in at least the first exposure step with actinic rays, and developing the photosensitive layer after the second exposure step, thereby forming a conductive pattern. A developing step to be formed. In the conductive pattern thus obtained, the conductive pattern 2a formed on the cured resin layer 3a can have a small step Ha.

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

The laminating step is performed by, for example, removing the protective conductive film or the supporting film from the photosensitive conductive film, if present, and then pressing the photosensitive resin layer or conductive film side to the substrate while heating. This operation is preferably performed under reduced pressure from the viewpoint of adhesion and followability. In the lamination of the photosensitive conductive film, the photosensitive layer or the substrate is preferably heated to 70 to 130 ° C., and the pressure is about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). Although preferred, these conditions are not particularly limited. In addition, if the photosensitive layer is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the base material in advance, but the base material can be pre-heated to further improve the laminating property. .

  In the exposure step of irradiating a predetermined portion of the photosensitive layer on the substrate with actinic rays with the support film attached, as an exposure method, a method of irradiating actinic rays in an image form through a negative or positive mask pattern called artwork ( Mask exposure method). A known light source is used as the active light source.

Exposure at the exposure step may vary depending on the composition of the device and the photosensitive resin composition ^used, it is preferably ^{5mJ / cm 2 ~1000mJ / cm 2} , is 10mJ / cm ² ~200mJ / cm 2 More preferred. In terms of excellent photocurability, it is preferably 10 mJ / cm ² or more, and in terms of resolution, it is preferably 1000 mJ / cm ² or less. The exposure process may be performed in two stages, and after the first stage is performed with the above-mentioned exposure amount, the second stage may be performed at 100 to 10,000 mJ / cm ² .

  The wet development is performed by a known method such as spraying, rocking immersion, brushing, or scrubbing using a developer corresponding to the photosensitive resin used, such as an alkaline aqueous solution, an aqueous developer, or an organic solvent developer.

  As the developing solution, a safe and stable solution having good operability such as an alkaline aqueous solution is used. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium or ammonium carbonate or bicarbonate; potassium phosphate, sodium phosphate and the like And alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate.

  As alkaline aqueous solution used for image development, sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium hydroxide aqueous solution, sodium tetraborate aqueous solution, etc. are preferable. The concentration of the alkaline aqueous solution is usually 0.1 to 5% by mass. Moreover, it is preferable to make pH of alkaline aqueous solution into the range of 9-11, and the temperature is adjusted according to the developability of the photosensitive resin layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.

  An aqueous developer composed of water or an aqueous alkali solution and one or more organic solvents can be used. Here, as the base contained in the alkaline aqueous solution, in addition to the above-mentioned bases, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3 -Propanediol, 1,3-diamino-2-propanol, morpholine and the like may be used.

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

  The aqueous developer preferably has an organic solvent concentration of 2 to 90% by mass, and the temperature can be adjusted according to the developability. Furthermore, the pH of the aqueous developer is preferably as low as possible within a range where the resist can be sufficiently developed, preferably pH 8-12, more preferably pH 9-10. In addition, a small amount of a surfactant, an antifoaming agent, or the like can be added to the aqueous developer.

  Examples of the organic solvent developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. These organic solvents preferably add water in the range of 1 to 20% by mass in order to prevent ignition.

  Examples of the development method include a dip method, a paddle method, a high-pressure spray method, brushing, and slapping. Among these, it is preferable to use a high-pressure spray system from the viewpoint of improving the resolution.

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

  According to the method for forming a conductive pattern of the present invention, it is possible to easily form a transparent conductive pattern on a substrate such as glass or plastic without forming an etching resist like an inorganic film such as ITO. is there.

  Although the base material with a conductive pattern of the present invention is obtained by the method for forming a conductive pattern described above, the surface resistivity of the conductive film or the conductive pattern may be 1000Ω / □ or less from the viewpoint that it can be effectively used as a transparent electrode. Preferably, it is 500Ω / □ or less, more preferably 300Ω / □ or less. The surface resistivity can be adjusted by, for example, the concentration of the conductive fiber or the dispersion of the organic conductor or the coating amount.

  In the substrate with a conductive pattern of the present invention, the minimum value of visible light transmittance in the wavelength region of 400 nm to 700 nm is preferably 80% or more, more preferably 85% or more, and 90% or more. More preferably. When the conductive pattern substrate satisfies such a condition, the visibility in a display panel or the like is further improved. The light transmittance can be adjusted by the concentration of the conductive fiber or the dispersion of the organic conductor and the coating amount. The transmittance can also be adjusted by the shape (fiber diameter and fiber length) of the conductive fiber. The thinner the fiber diameter, the higher the transmittance.

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

  FIG. 6 is a schematic top view illustrating an example of a capacitive touch panel sensor. FIG. 6 shows an example of a capacitive touch panel sensor that includes 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, may be laminated on the transparent substrate 101, and may be disposed so as to sandwich the transparent substrate 101 therebetween.

  In the capacitive touch panel, the transparent electrodes 103 and 104 have lead-out wires (not shown) for connecting to a control circuit of a driver element circuit that controls an electric signal.

  In the touch panel sensor according to this embodiment, at least one of the transparent electrodes is formed using the photosensitive conductive film of the present invention. In this case, the other transparent electrode may be formed in advance on a transparent substrate by a known method using a transparent conductive material.

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

The components used in Examples and Comparative Examples are as follows.
(B) component, trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "TMPTA")

Component (C) 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (trade name “OXE-01” manufactured by BASF Corporation)
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (BASF Corporation, trade name “LUCIRIN TPO”)
2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF Corporation, trade name “Irgacure 651”)

Component (D): ethyl 2-cyano-3,3-diphenylacrylate (manufactured by Cypro Kasei Co., Ltd., trade name “SEESORB501”)
2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole (trade name “RUVA-93” manufactured by Otsuka Chemical Co., Ltd.)
・ Polymer type UV absorber (manufactured by Daiwa Kasei Co., Ltd., trade name “PUVA-50M-50K”)

・ Carbon nanotubes (Hipco single-walled carbon nanotube high-purity product, manufactured by Unidym)
・ Dodecyl-pentaethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.)

(Other ingredients)
Octamethylcyclotetrasiloxane (trade name “SH-30” manufactured by Toray Dow Corning Co., Ltd.) (leveling agent)
・ Methyl ethyl ketone (manufactured by Tonen Chemical Co., Ltd.) (solvent)

Production Example 1
<Preparation of silver fiber dispersion (conductive fiber dispersion (coating liquid for forming conductive film))>
[Preparation of silver fiber by polyol method]
In a 2000 mL three-necked flask, 500 mL of ethylene glycol was added and heated to 160 ° C. using an oil bath while stirring with a magnetic stirrer under a nitrogen atmosphere. A separately prepared solution 1 (a solution in which 2 mg of PtCl ₂ was dissolved in 50 mL of ethylene glycol) was added dropwise thereto. After 4 to 5 minutes, 5 g of solution 2 (a solution in which 5 g of AgNO ₃ was dissolved in 300 mL of ethylene glycol) and 5 g of solution 3 (polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight: 58000)) were added to 150 mL of ethylene glycol. The dissolved solution was dropped from each dropping funnel over 1 minute, and the reaction solution was stirred at 160 ° C. for 60 minutes.

  The reaction solution was allowed to stand at 30 ° C. or lower and then diluted 10 times with acetone. The diluted solution of the reaction solution was centrifuged at 2000 rpm for 20 minutes using a centrifuge, 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, it centrifuged twice similarly using distilled water, and obtained the silver fiber. When the obtained silver fiber was observed with an optical microscope, the fiber diameter (diameter) was 30 nm, and the fiber length was 3 μm.

[Preparation of silver fiber dispersion]
In pure water, the silver fiber obtained above is dispersed so that the concentration is 0.2% by mass, and dodecyl-pentaethylene glycol is dispersed so that the concentration is 0.1% by mass. Got.

<Preparation of carbon nanotube dispersion>
A high purity product of Unipym's Hipco single-walled carbon nanotubes is dispersed in pure water at a concentration of 0.4% by mass, and dodecyl-pentaethylene glycol as a surfactant is dispersed at a concentration of 0.1% by mass. A dispersion was obtained.

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

Production Example 3
<Preparation of polymer type ultraviolet absorber (D1) solution>
A flask equipped with a stirrer, reflux condenser, inert gas inlet and thermometer was charged with (1) shown in Table 2 and heated to 80 ° C. in a nitrogen gas atmosphere. While maintaining the reaction temperature at 80 ° C. ± 2 ° C., (2) shown in Table 2 was uniformly added dropwise over 4 hours. After the dropwise addition of (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours to obtain a polymer type ultraviolet absorber (D1) solution (solid content 50% by mass) having a weight average molecular weight of 15000. The acid value of the polymer type ultraviolet absorber (D1) was 0 mgKOH / g.

  The characteristics of the prepared polymer solution were measured by the following method.

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

Pump: Hitachi L-6000 type (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)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (trade name, manufactured by Hitachi, Ltd.)

(2) Acid value The acid value was measured as follows. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile components, thereby obtaining a solid polymer. Then, after precisely weighing 1 g of the solid polymer, the precisely weighed polymer was put into an Erlenmeyer flask, and 30 g of acetone was added and dissolved uniformly. Next, an appropriate amount of an indicator, phenolphthalein, was added to the solution, and titration was performed using a 0.1N aqueous KOH solution. And the acid value was computed by following Formula.
Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100)
In the formula, Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the mass (g) of the measured resin solution, and I represents the proportion (mass%) of the non-volatile content in the measured resin solution. The acid value of the polymer type ultraviolet absorber (D1) was also calculated by the same operation.

(3) Glass transition temperature (Tg)
The prepared binder polymer solution was uniformly applied onto a polyethylene terephthalate film (trade name “Purex A53” manufactured by Teijin DuPont Films Ltd.), and dried for 10 minutes with a hot air convection dryer at 90 ° C. A film made of a binder polymer having a thickness of 40 μm after drying was formed. Next, using an exposure machine having a high pressure mercury lamp (trade name “EXM-1201” manufactured by Oak Manufacturing Co., Ltd.), the amount of irradiation energy is 400 mJ / cm ² (measured value at i-line (wavelength 365 nm)). The film was exposed. The exposed film was heated on a hot plate at 65 ° C. for 2 minutes, then at 95 ° C. for 8 minutes, heated at 180 ° C. for 60 minutes in a hot air convection dryer, and then peeled off from the polyethylene terephthalate film, Using TMA / SS6000 (manufactured by Seiko Instruments Inc.), the coefficient of thermal expansion of the cured film is measured when the temperature is increased at a temperature rising rate of 5 ° C./min, and the inflection point obtained from the curve is the glass transition. It calculated | required as temperature Tg.

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

[Preparation of Photosensitive Resin Composition Solution X1]
The materials shown in Table 3 were mixed at the blending amounts (parts by mass) shown in Table 3 for 15 minutes using a stirrer to produce a photosensitive resin composition solution X1. (A) The compounding quantity of a component is the mass of solid content.

[Preparation of photosensitive conductive film V1]
The solution X1 of the photosensitive resin composition was uniformly applied on the conductive film W1, and dried for 10 minutes with a hot air convection dryer at 100 ° C. to form a photosensitive resin layer. Thereafter, the photosensitive resin layer was covered with a polyethylene film (trade name “NF-13” manufactured by Tamapoly Co., Ltd.) 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]
While peeling off the polyethylene film of the obtained photosensitive conductive film V1, a laminator (manufactured by Hitachi Chemical Co., Ltd., trade name “HLM-3000 type”) is placed so that the photosensitive resin layer is in contact with the glass substrate having a thickness of 1 mm. Using a roll temperature of 110 ° C., a substrate feed speed of 1 m / min, and a pressure bonding pressure (cylinder pressure) of 4 × 10 ⁵ Pa (thickness of 1 mm, length of 10 cm × width of 10 cm, the linear pressure at this time was 9 .8 × 10 ³ N / m) to produce a substrate in which a photosensitive conductive film V1 including a support film was laminated on a glass substrate.

Next, using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.) on the photosensitive conductive film on the glass substrate, an exposure amount of 5 × 10 ² J / m ² (i-line (wavelength) from the support film side. The measured value at 365 nm) was irradiated with ultraviolet rays. Thereafter, the support film is removed, and further irradiated with ultraviolet rays at an exposure amount of 1 × 10 ⁴ J / m ² (measured value at i-line (wavelength 365 nm)) from the conductive film side with a parallel light exposure machine, and a photosensitive resin layer And a sample for measuring transmittance of the conductive film (photosensitive layer) (film thickness: 5.0 μm).

  Next, using the ultraviolet-visible spectrophotometer (trade name “U-3310”, manufactured by Hitachi Instrument Service Co., Ltd.), the obtained sample was measured for the ultraviolet light transmittance in the measurement wavelength range of 300 to 380 nm, and the measurement wavelength. Visible light transmittance was measured in the region of 400-700 nm. In addition, the transmittance | permeability in the photosensitive conductive film independent was measured for the glass substrate as the 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 value of the visible light transmittance in the wavelength region of 400 nm or more and 700 nm or less was 87%, and good transmittance was secured. The ultraviolet light transmittance was 71% at 380 nm and 15% at 300 nm. The maximum value of the ultraviolet light transmittance at 300 to 380 nm was 71%.

[Measurement of surface resistivity of photosensitive conductive film V1]
In the same manner as the method for measuring the light transmittance of the photosensitive conductive film V1, a sample for measuring the surface resistivity in which the photosensitive conductive film V1 was laminated on the glass substrate was produced. The surface resistivity of the sample was measured by a non-contact resistance measuring instrument (trade name “EC-80P” manufactured by Napson Co., Ltd.) and found to be 100 ± 5Ω / □.

[Measurement of sensitivity of photosensitive conductive film V1]
Laminator (Hitachi Chemical Co., Ltd.) so that the photosensitive resin layer is in contact with the easy-adhesion surface of the PET film substrate (thickness 50 μm, manufactured by Toyobo, trade name “A4100”) while peeling the polyethylene film of the photosensitive conductive film V1. Manufactured under the trade name “HLM-3000 type”) and laminated on a PET film substrate under the conditions of a roll temperature of 110 ° C., a substrate feed rate of 1 m / min, and a pressure (cylinder pressure) of 4 × 10 ⁵ Pa. A film substrate on which a photosensitive conductive film V1 including a support film was laminated was produced.

Next, a 41-step tablet (manufactured by Hitachi Chemical Co., Ltd.) is brought into close contact with the support film 1 of the photosensitive conductive film on the film substrate as a photomask, and a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd., trade name “EXM1201”). )) From the support film 1 side and exposed through a photomask. The exposure amount was 4 × 10 ² J / m ² (measured value at i-line (wavelength 365 nm)). After the exposure, the substrate was allowed to stand at room temperature (23 ° C. to 25 ° C.) for 15 minutes, and then the support film 1 was removed, followed by development by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 30 seconds. By development, a conductive pattern of the photosensitive conductive film was formed on the cured resin pattern. The sensitivity was evaluated based on the number of remaining steps after development. When the sensitivity of the photosensitive conductive film V1 was evaluated, it was 8 steps. The higher the number of steps of the remaining step tablet (the higher the numerical value), the higher the sensitivity.

[Measurement of resolution of photosensitive conductive film V1 (full development process)]
Laminator (Hitachi Chemical Co., Ltd.) so that the photosensitive resin layer is in contact with the easy-adhesion surface of the PET film substrate (thickness 50 μm, manufactured by Toyobo, trade name “A4100”) while peeling the polyethylene film of the photosensitive conductive film V1. Manufactured under the trade name “HLM-3000 type”) and laminated on a PET film substrate under the conditions of a roll temperature of 110 ° C., a substrate feed rate of 1 m / min, and a pressure (cylinder pressure) of 4 × 10 ⁵ Pa. A film substrate on which a photosensitive conductive film V1 including a support film was laminated was produced.

  Next, a photomask made of PET having a wiring pattern with a line width / space width of 6/6 to 47/47 (unit: μm) is brought into close contact with the support film 1 of the photosensitive conductive film on the film substrate, and parallel rays Using an exposure machine (trade name “EXM1201” manufactured by Oak Seisakusho Co., Ltd.), exposure was performed from the support film 1 side through a photomask. The exposure amount was an exposure amount at which the sensitivity of a 41-step tablet (manufactured by Hitachi Chemical Co., Ltd.) was 8 steps. After the exposure, the substrate was allowed to stand at room temperature (23 ° C. to 25 ° C.) for 15 minutes, and then the support film 1 was removed, followed by development by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 30 seconds. By observing the conductive pattern after development with an optical microscope, the conductive layer in the unexposed area could be removed cleanly by the development process, and the conductive pattern could be formed without the exposed area being missing. The resolution was evaluated by the smallest value of the line width / space width. It was 25 micrometers when the resolution of the photosensitive conductive film V1 was evaluated. The evaluation of resolution means that the smaller the numerical value, the better.

[Measurement of resolution of photosensitive conductive film V1 (low step development process)]
A laminator (Hitachi Chemical Co., Ltd.) is made so that the photosensitive resin layer is in contact with the easy-adhesion surface of a PET film substrate (thickness 50 μm, manufactured by Toyobo, trade name “A4100”) while peeling the polyethylene film of the photosensitive conductive film V1. Manufactured under the trade name “HLM-3000 type”) and laminated on a PET film substrate under the conditions of a roll temperature of 110 ° C., a substrate feed rate of 1 m / min, and a pressure (cylinder pressure) of 4 × 10 ⁵ Pa. A film substrate on which a photosensitive conductive film V1 including a support film was laminated was produced.

  Next, a photomask made of PET having a wiring pattern with a line width / space width of 6/6 to 47/47 (unit: μm) is brought into close contact with the support film 1 of the photosensitive conductive film on the film substrate, and parallel rays Using an exposure machine (Oak Seisakusho Co., Ltd., trade name “EXM1201”), exposure was performed from the support film 1 side through a photomask (first stage exposure). The exposure amount was an exposure amount at which the sensitivity of a 41-step tablet (manufactured by Hitachi Chemical Co., Ltd.) was 8 steps. Next, the photomask and the support film 1 were removed, and further, the entire surface of the film was exposed in the atmosphere (in the presence of oxygen) from above the conductive layer of the photosensitive conductive film (second stage exposure). The exposure amount was set to be three times the exposure amount of the first stage exposure.

  After exposure, the film was allowed to stand at room temperature (23 ° C. to 25 ° C.) for 15 minutes, and then developed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 30 seconds. By observing the developed conductive pattern with an optical microscope, the conductive fiber of the conductive layer can be removed cleanly at the part that was unexposed during the first stage exposure by the development process, and the first stage exposure. The resolution was evaluated by the smallest value of the line width / space width in which the conductive fiber pattern could be formed without missing in the exposed portion at times. When the resolution of the photosensitive conductive film V1 was evaluated, it was 20 μm. The evaluation of resolution means that the smaller the numerical value, the better.

Examples 2-6
Except having used the solution (X) of the photosensitive resin composition shown in Table 4, the photosensitive conductive film was produced similarly to Example 1 and various characteristics were evaluated. The results are shown in Table 4.

Examples 7 and 8
Except having used the conductive film W2 or W3 instead of the conductive film W1, the photosensitive conductive film was produced similarly to Example 1 and various characteristics were evaluated. The results are shown in Table 4. The production methods of the conductive films W2 and W3 are as follows.

[Preparation of conductive film (conductive film of photosensitive conductive film) W2]
The silver fiber dispersion obtained in Production Example 1 above was uniformly applied at 20 g / m ² on a polyethylene terephthalate film (PET film, manufactured by Teijin Ltd., trade name “G2-50”) having a thickness of 50 μm, The film was dried with 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.

[Preparation of conductive film (conductive film of photosensitive conductive film) W3]
The carbon nanotube dispersion obtained in Production Example 1 above was uniformly applied at 30 g / m ² on a 50 μm thick polyethylene terephthalate film (PET film, manufactured by Teijin Ltd., trade name “G2-50”), The film was dried with a hot air convection dryer at 100 ° C. for 3 minutes to form a conductive film W3. The thickness of the conductive film after drying was 0.05 μm.

Comparative Examples 1-3
Except having used the solution (X) of the photosensitive resin composition shown in Table 5, the photosensitive conductive film was produced similarly to Example 1, and various characteristics were evaluated. The results are shown in Table 5.

Comparative Example 4
A photosensitive conductive film was prepared in the same manner as in Example 1 except that the conductive film W3 was used instead of the conductive film W1 and the photosensitive resin composition solution (X) shown in Table 5 was used. Characteristics were evaluated. The results are shown in Table 5.

  As shown in Tables 4 and 5, it was confirmed that the resolution was improved by using a photosensitive layer containing an ultraviolet absorber as the component (D). More specifically, Examples 1 to 7 in which the photosensitive layer contains silver nanowires show superior resolution compared to Comparative Examples 1 to 3, and Example 8 in which the photosensitive layer contains carbon nanotubes is Comparative Example 4. It was confirmed that an excellent resolution was shown.

  When the photosensitive conductive film of the present invention is used, a conductive pattern can be formed with sufficient resolution even when the photosensitive layer contains conductive fibers. Moreover, it can use for manufacture of the touchscreen containing preparation of the base material with a conductive pattern which has sufficient resolution, and a base material with a conductive pattern.

  DESCRIPTION OF SYMBOLS 1 ... Support film, 2 ... Conductive film, 2a ... Conductive pattern, 3 ... Photosensitive resin layer, 3a ... Resin hardened layer, 3b ... Resin hardened pattern, 4 ... Photosensitive layer, 5 ... Protective film, 6 ... Mask pattern, 10 , 12 ... photosensitive conductive film, 20 ... base material, 40, 41, 42 ... base material with conductive pattern, 101 ... transparent base material, 102 ... touch screen, 103 ... transparent electrode (X position coordinate), 104 ... transparent electrode (Y position coordinate).

Claims (9)

A support film, and a photosensitive layer provided on the support film,
The photosensitive conductive film in which the said photosensitive layer contains a conductive fiber, a binder polymer, a photopolymerizable compound, a photoinitiator, and a ultraviolet absorber.   The photosensitive conductive film according to claim 1, wherein the ultraviolet absorber has a maximum absorption wavelength in a wavelength range of 250 nm to 400 nm.   The photosensitive conductive film of Claim 1 or 2 whose 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 as described in any one of Claims 1-3 in which the said ultraviolet absorber has a thermopolymerizable group or a photopolymerizable group.   The photosensitive conductive film as described in any one of Claims 1-3 whose said ultraviolet absorber is a polymer type ultraviolet absorber.   The photosensitive conductive film as described in any one of Claims 1-5 whose said conductive fiber is silver fiber. Transferring the photosensitive layer of the photosensitive conductive film according to any one of claims 1 to 6 onto a substrate;
An exposure step of irradiating the photosensitive layer transferred onto the substrate with actinic rays in a pattern;
A development step of forming a conductive pattern by removing an unexposed portion of the photosensitive layer;
A method for forming a conductive pattern.   The base material with a conductive pattern which has a base material and the conductive pattern formed by the method of Claim 7 on the said base material.   A touch panel sensor comprising the substrate with a conductive pattern according to claim 8.

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