Transparent conductive substrate and double-side photolithographic method using the same

Abstract

To provide a transparent conductive substrate and a double-side photolithographic method using the same.SOLUTION: The present invention provides a transparent conductive substrate, sequentially including a first resist layer, a first transparent conductive layer, a transparent core, a second transparent conductive layer and a second resist layer; where the first resist layer comprises a UV-light sensitive composition (C1); and the second resist layer comprises a visible-light sensitive composition (C2). The present invention provides a double-side photolithographic method for manufacturing transparent conductive laminates. The transparent conductive laminates manufactured by the method may be incorporated into touch panels.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a transparent conductive substrate and a double-sided method for simultaneously forming conductive patterns on both sides of the transparent conductive substrate. [Background technology]

[0002] Photosensitive compositions are well known to be used in the manufacture of printed circuits, in the formation of photolithographic printed boards, and in waterproofing applications. Regardless of the various applications, the main function of the photosensitive composition is to form a resist pattern. One common process of forming a resist pattern from a negative photosensitive composition typically includes the steps of i) applying the photosensitive composition onto a substrate, ii) imagewise exposing to actinic radiation, and iii) developing to form a resist pattern. After etching or plating to form a conductive pattern, the hardened resist pattern is generally peeled off from the processed substrate. To improve production efficiency, two unique resist patterns can be simultaneously formed on each side of an opaque substrate by a double-sided photolithography process. The double-sided photolithography process includes the steps of forming a resist layer on each side of a substrate, either sequentially or simultaneously, followed by imagewise exposing, developing, etching or stripping, and simultaneously stripping.

[0003] Recently, touch panels (i.e., display devices with touch sensors) have been widely applied in various electronic devices, such as mobile phones, personal digital assistants (PDAs), navigation devices, etc. Known touch sensors can be categorized as resistive or capacitive. In particular, capacitive touch sensors can receive multiple touches and are widely used for use in mobile devices and the like. The basic technology of capacitive touch sensors works off on electrostatic fields generated by layers of individually etched conductive materials to form an xy conductive grid.

[0004] For touch panel applications, touch sensors require precise alignment of different circuit patterns on both sides of a transparent core, and the circuit patterns can be formed sequentially by photolithography. However, given the optically transparent nature of the substrate and some transparent conductor materials, such as indium tin oxide (ITO), double-sided photolithography is not applicable, because the actinic radiation used to expose the resist on one side of the transparent core and / or transparent conductive layer will also inevitably expose the photoresist on the opposite side of the transparent core. As a result, the same pattern will inevitably be formed on both sides of the transparent core. However, for touch panel applications, it requires having different circuit patterns (i.e., xy conductive grids) on both sides of the transparent core.

[0005] In (Patent Document 1), H. Kobayashi discloses a method for producing a transparent conductive laminate by using a transparent core containing an ultraviolet absorbing agent or by applying an ultraviolet absorbing adhesive layer between two transparent cores. The disadvantages of this method include the change in transparency and thickness of the transparent conductive laminate produced therefrom, as well as the mechanical strength, chemical resistance, and electrical conductivity.

[0006] R. Petcavich et al. also disclose a method for forming circuits on both sides of a transparent core in (Patent Document 2). The method for manufacturing a touch sensor includes the steps of applying a UV absorbing layer to one side of the transparent core; then applying a first photoresist layer onto the UV absorbing layer on one side and a second photoresist layer directly onto the opposite side of the transparent core; photopatterning both photoresist layers using UV radiation; and forming conductive circuits on the two sides of the transparent core. One obvious disadvantage of this method is that by adding a UV absorbing layer (i.e., 10-15 microns), the touch sensor manufactured therefrom will have an increased overall thickness. Needless to say, these touch sensors may have problems with reduced visibility. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] US Patent Application Publication No. 20110151215 A1 [Patent Document 2] US Patent Application Publication No. 20210318769 A1 [Patent Document 3] U.S. Pat. No. 5,662,707 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention addresses the above-mentioned problems by providing a photosensitive composition, and a dry film produced therefrom, that has excellent tunability in terms of photosensitivity and can be photocured by exposure to different light beams at the same time. As a result, a double-sided photolithography process can be applied to produce transparent conductive laminates without introducing extra layers or light blocking / absorbing materials into the resulting laminate. Furthermore, the transparency, mechanical strength, chemical resistance, and electrical conductivity of the conductive substrate remain unchanged. [Means for solving the problem]

[0009] A first aspect of the present invention provides a transparent conductive substrate for producing a transparent conductive laminate comprising, in sequence, a first resist layer, a first transparent conductive layer, a transparent core, a second transparent conductive layer, and a second resist layer. And, The transparent core has a total transmittance (T 400 ~ 800 ) ; a first resist layer comprising a UV radiation sensitive composition; a second resist layer comprising a visible light sensitive composition; The UV radiation sensitive composition undergoes photopolymerization upon exposure to light with a wavelength of less than 400 nm; The visible light sensitive composition undergoes photopolymerization upon exposure to light in the wavelength range of 400 nm to 800 nm. It is a circuit board.

[0010] A second aspect of the present invention is a method for producing a transparent conductive substrate, comprising the steps of: (i) providing a transparent core; (ii) forming a first transparent conductive layer on one surface of the transparent core; (iii) forming a second transparent conductive layer on an opposite surface of the transparent core; (iv) applying a UV-ray sensitive composition (C1) onto the first transparent conductive layer to form a first resist layer; (v) applying a visible light sensitive composition (C2) onto the second transparent conductive layer to form a second resist layer; The method includes:

[0011] A third aspect of the present invention is a double-sided photolithography method for producing a transparent conductive laminate, comprising: (A) providing a transparent conductive substrate of the present invention; (B) simultaneously exposing the first resist layer to a first light source and the second resist layer to a second light source; (C) simultaneously developing the first resist pattern and the second resist pattern by removing unexposed portions of each resist layer; (D) simultaneously etching portions of the first transparent conductive layer and the second transparent conductive layer that are not protected by their respective resist patterns; (E) simultaneously peeling off the first resist pattern and the second resist pattern to obtain a transparent conductive laminate; Includes; Where: the transparent conductive laminate comprises a first conductive circuit and a second conductive circuit on each side of a transparent core, the design patterns of the first conductive circuit and the second conductive circuit being different from each other; the first light source and the second light source are disposed on opposite sides of a transparent conductive substrate; a first light source irradiates light at a wavelength of less than 400 nm and at a target exposure energy for patterning the first resist layer, such that the second resist layer is substantially free of being patterned by the first light source; The second light source irradiates light at a wavelength between 400 nm and 800 nm and at a target exposure energy for the second resist layer, such that the first resist layer is not substantially patterned by the light irradiated by the second light source.

[0012] Embodiments of the present disclosure are illustrated by way of example and without limitation in the accompanying figures of the accompanying drawings in which like reference symbols indicate similar elements and in which: [Brief description of the drawings]

[0013] [Figure 1] 1 is a side view illustrating a transparent conductive substrate according to some embodiments of the present invention. [Diagram 2] 1 is a side view illustrating a transparent conductive substrate according to some embodiments of the present invention. [Diagram 3] FIG. 2 illustrates an example of a double-sided photolithography method for producing a transparent conductive laminate according to an embodiment of the present invention. [Figure 4] Photographs taken of the first side of the transparent conductive laminates fabricated by the double-sided photolithography method of the present invention, Figure 4A shows the processed transparent conductive substrate of E2, Figure 4B shows the processed transparent conductive substrate of E7, and Figure 4C shows the processed transparent conductive substrate of CE5. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] All publications, patent applications, patents, and other references mentioned herein are expressly incorporated by reference herein in their entirety for all purposes as if fully set forth, unless otherwise noted.

[0015] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflicts, the present specification, including definitions, will control.

[0016] Unless otherwise stated, all percentages, parts, ratios, etc. are by weight.

[0017] As used herein, the term "produced from" is synonymous with "comprising." As used herein, the terms "comprise," "including," "including," "including," "having," "having," "containing," or "containing," or any other variation thereof, are intended to cover non-exclusive inclusions. For example, a composition, process, method, article, or device that includes a list of elements is not necessarily limited to only those elements and may include other elements not expressly listed or inherent to such composition, process, method, article, or device.

[0018] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. When in a claim, such a phrase would exclude the inclusion from the claim of materials other than those recited, except for impurities ordinarily associated therewith. When the phrase "consisting of" appears in a clause in the body of a claim, rather than immediately following a preamble, it limits only the elements specified in that clause; other elements are not excluded from the claim as a whole.

[0019] The transitional phrase "consisting essentially of" is used to define a composition, method, or apparatus that includes materials, steps, features, components, or elements in addition to those literally contemplated, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristics of the claimed invention. The term "consisting essentially of" occupies the intermediate region between "comprising" and "consisting of."

[0020] The term "comprising" is intended to include embodiments encompassed by the terms "consisting essentially of" and "consisting of. Similarly, the term "consisting essentially of" is intended to include embodiments encompassed by the term "consisting of.

[0021] When an amount, concentration, or other value or parameter is given as either a range, a preferred range, or a list of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed from any pairing of any upper range limit or preferred value with any lower range limit or preferred value, whether or not the ranges are separately disclosed. For example, if a range of "1 to 5" is recited, the recited range should be interpreted as including the ranges "1 to 4," "1 to 3," "1 to 2," "1 to 2 and 4 to 5," "1 to 3 and 5," etc. When a range of numerical values ​​is recited herein, unless otherwise specified, the range is intended to include the endpoints thereof, as well as all integers and fractions within the range.

[0022] As used herein, the terms "a" and "an" include the concepts of "at least one" and "one or more." Unless otherwise specified, all percentages, parts, ratios, etc. are by weight.

[0023] When the term "about" is used to describe a value or an endpoint of a range, the disclosure should be understood to include the specific value or endpoint referred to.

[0024] Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not an exclusive "or." For example, a condition A "or" B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and A and B are both true (or exist).

[0025] The term "substantially free" refers to less than 5%, or less than 3%, or less than 1% of the resist being patterned.

[0026] The term "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, and the term "(meth)acrylate" refers to the acrylate or the corresponding methacrylate. Similarly, the term "(meth)acryloyloxy group" refers to the acryloyloxy group or the methacryloyloxy group. The term "(poly)ethyleneoxy" refers to at least one of an ethyleneoxy group or a polyethyleneoxy group in which two or more ethylene groups are bonded via ether bonds. An ethyleneoxy group is a group represented by (-CH2CH2-O-), and is also referred to as an "oxyethylene group" or "ethylene oxide". The term "(poly)propyleneoxy group" as used herein refers to at least one of a propyleneoxy group or a polypropyleneoxy group in which two or more propylene groups are bonded via ether bonds. The propyleneoxy group is a group represented by (-CHCH3CH2-O-), a group represented by (-CH2CHCH3-O-), or a group represented by (-CH2CH2CH2-O-), and is also called an "oxypropylene group" or "propylene oxide". The term "EO-modified" compound means a compound having a (poly)ethyleneoxy group; "PO-modified" compound means a compound having a (poly)propyleneoxy group; "EO, PO-modified" compound means a compound having both a (poly)ethyleneoxy group and a (poly)propyleneoxy group.

[0027] The terms "sheet," "layer," and "film" are used interchangeably in their broad senses.

[0028] The embodiments of the present invention include any of the embodiments described herein and may be combined in any manner, and the descriptions of variables in the embodiments relate not only to the photosensitive composition of the present invention but also to the photosensitive dry film made therefrom.

[0029] The invention is described in detail herein below.

[0030] (Transparent conductive substrate) 1 is a side view of a transparent conductive substrate according to some embodiments of the present invention. The transparent conductive substrate 100 includes, in sequence, a first resist layer 31, a first transparent conductive layer 21, a transparent core 10, a second transparent conductive layer 22, and a second resist layer 32.

[0031] With respect to a transparent conductive substrate, "transparent" may refer to the ability to transmit a substantial portion of visible light through the substrate. In some applications, "transparent" refers to a total transmittance (T) in the range of 400 nm to 800 nm that is 60% or greater, or 70% or greater. 400~800 ), however, other transmittance values, such as 75% or greater, may be desirable for touch sensor applications.

[0032] A wide variety of transparent cores can be used in the transparent conductive substrate of the present invention. For example, the transparent core can be a sheet of glass, flexible glass, or quartz; or a polymer film composed of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), cellulose acetate, polyethylene (PE), polypropylene (PP), cyclic polyolefins, poly(meth)acrylate esters, polyacrylates, polyamides, polyimides, polycarbonates, poly(ether sulfones), polysulfones, or combinations thereof.

[0033] The transparent core 10 generally has a thickness of 1 μm to 200 μm, or 5 μm to 100 μm, or 10 μm to 50 μm.

[0034] First transparent conductive layer 21 and second transparent conductive layer 22 each independently comprise a conductive material that generally has a resistance value in the range of 10 ohms to 150 ohms.

[0035] The conductive material is not particularly limited, but examples thereof include metal oxide particles such as zinc oxide, barium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), indium gallium zinc oxide (IGZO), zirconium oxide, ytterbium oxide, yttrium oxide, tantalum oxide, aluminum oxide, cerium oxide, and titanium oxide. Among them, ITO, IZO, and IGZO are particularly preferred in terms of achieving both high transparency and conductivity. Typically, the metal oxide particles preferably have a particle size of 10 μm or less, or 1.0 μm or less, or 50 nm to 150 nm.

[0036] Other suitable conductive materials include carbon nanotubes and metal nanowires, which are wire-like conductive metals. Specific examples of metals for metal nanowires include iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, cadmium, osmium, iridium, platinum, and gold. Copper, silver, platinum, and gold nanowires are preferred in terms of electrical conductivity. Each of the metal nanowires has at least one cross-sectional dimension less than 500 nm, or less than 200 nm, or less than 100 nm. Each of the metal nanowires has an aspect ratio greater than 10, or greater than 50, or greater than 100. The shape and size of each metal nanowire can be measured using a scanning electron microscope or a transmission electron microscope.

[0037] In one embodiment of the invention, each of the first transparent conductive layer and the second transparent conductive layer independently contains a conductive material selected from the group consisting of indium tin oxide, indium zinc oxide, indium gallium zinc oxide; carbon nanotubes; and nanowires of copper, silver, platinum, or gold.

[0038] The conductive materials constituting the first transparent conductive layer 21 and the second transparent conductive layer 22 may be the same or different. When the conductive materials constituting the transparent conductive layers 21 and 22 are the same, the transparent conductive layers 21 and 22 may be formed simultaneously on both sides of the transparent core 10. The first conductive layer 21 and the second transparent conductive layer 22 of the present invention may be formed by applying a dispersion containing the conductive material onto one or both surfaces of the transparent core 10 by spin coating, dipping, or chemical vapor deposition (CVD).

[0039] Each transparent conductive layer 21 or 22 has a thickness of 0.001 μm to 10 μm, or 0.01 μm to 7 μm, or 0.1 μm to 5 μm.

[0040] (resist layer) The first resist layer 31 is composed of a UV-ray sensitive composition (C1), which is patterned by exposing it to light having a wavelength of less than 400 nm. The second resist layer 32 is composed of a visible light sensitive composition (C2), which is patterned by exposing it to light in the wavelength range of 400 nm to 800 nm.

[0041] The UV-sensitive composition (C1) comprises (a) 30 to 70% by weight of an alkali-soluble polymer; (b) 10 to 70% by weight of a polymerizable compound having an ethylenically unsaturated double bond; (c) 0.1 to 20 wt. % of a photoinitiator; (d1) 0 to 20% by weight of a UV absorbing sensitizer having a maximum absorption in the UV radiation region; (e) 0 to 20 wt. % of other additives; (f) 0 to 20 weight percent of a visible light blocking material that absorbs incident visible light energy; Includes.

[0042] The visible light sensitive composition (C2) is (a) 30 to 70% by weight of an alkali-soluble polymer; (b) 10 to 70% by weight of a polymerizable compound having an ethylenically unsaturated double bond; (c) 0.1 to 20 wt. % of a photoinitiator; (d2) 0.01 to 20% by weight of a visible light absorbing sensitizer having a maximum absorption in the visible light region; (e) 0 to 20 wt. % of other additives; (g) 0.01 to 20 weight percent of a UV ray blocking material by absorbing incident UV ray energy; Includes.

[0043] Hereinafter, each component contained in the UV radiation sensitive composition and / or visible light sensitive composition of the present disclosure will be described.

[0044] (Alkali-soluble copolymer (a)) As component (a), the alkali-soluble polymer is generally a polymer having an acid group (e.g., a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group). Preferably, the alkali-soluble polymer is derived from a polymerizable precursor containing a carboxylic acid group. Examples of polymerizable precursors containing a carboxylic acid group include (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, propiolic acid; maleic anhydride, phthalic anhydride, itaconic anhydride, citraconic anhydride, etc. In consideration of cost and solubility, (meth)acrylic acid is preferred.

[0045] The alkali-soluble polymer (a) may also contain structural units derived from a polymerizable precursor that does not have a carboxylic acid group.

[0046] Examples of polymerizable precursors having no carboxylic acid group include (meth)acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, citraconic acid diesters, (meth)acrylamides, vinyl ethers, esters of vinyl alcohol, styrene, substituted styrenes, (meth)acrylonitrile, vinyl-substituted heterocyclic compounds, N-vinyl amides, sulfonic acids having a vinyl group, phosphoric acid esters having a vinyl group, urethanes having a vinyl group, ureas having a vinyl group, sulfonamides having a vinyl group, phenols having a vinyl group, and imides having a vinyl group.

[0047] Examples of (meth)acrylate esters include alkyl (meth)acrylates, cycloalkyl (meth)acrylates, benzyl (meth)acrylates, etc. The alkyl (meth)acrylates are preferably esters of alkyl groups having 1 to 5 carbon atoms. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and mixtures thereof.

[0048] Examples of other (meth)acrylate esters include furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, iobomyloxyethyl (meth)acrylate, cyclohexyloxyethyl (meth)acrylate, adamantyloxyethyl (meth)acrylate, dicyclopentenyloxypropyloxyethyl (meth)acrylate, and the like.

[0049] In one embodiment, the alkali-soluble polymer (a) is derived from a mixture consisting of 15 to 50% by weight of styrene or substituted styrene; 15 to 35% by weight of (meth)acrylic acid; and 10 to 70% by weight of one or more (meth)acrylate esters, based on the total weight of the polymerizable precursors for constituting the alkali-soluble polymer (a).

[0050] In another embodiment, the alkali-soluble polymer (a) is derived from a mixture consisting of 15 to 45% by weight of styrene or substituted styrene, 20 to 30% by weight of (meth)acrylic acid, and 15 to 65% by weight of one or more (meth)acrylate esters, based on the total weight of the polymerizable precursors for constituting the alkali-soluble polymer (a).

[0051] In yet another embodiment, the alkali-soluble polymer (a) is derived from a mixture consisting of 10-45% by weight of styrene or substituted styrene, 20-30% by weight of (meth)acrylic acid, 10-60% by weight of benzyl (meth)acrylate, and 10-50% by weight of an alkyl (meth)acrylate ester, based on the total weight of the polymerizable precursors for constituting the alkali-soluble polymer (a).

[0052] The alkali-soluble polymer (a) can be obtained, for example, by radical polymerization of a mixture composed of styrene or α-methylstyrene, (meth)acrylic acid, one or more (meth)acrylate esters, and optionally other polymerizable precursors, using conventional methods.

[0053] The weight average molecular weight (Mw) of the polymer binder measured by gel permeation chromatography (GPC) (calculated based on a calibration curve prepared using polystyrene standards) is preferably 25,000 to 100,000, more preferably 30,000 to 80,000, and most preferably 40,000 to 60,000.

[0054] The dispersity (weight average molecular weight / number average molecular weight, Mw / Mn) of the alkali-soluble polymer (a) is preferably 3.0 or less, more preferably 2.8 or less, and even more preferably 2.5 or less.

[0055] The acid value of the alkali-soluble polymer (a) is preferably 90 mgKOH / g to 250 mgKOH / g, more preferably 100 mgKOH / g to 240 mgKOH / g, and even more preferably 120 mgKOH / g to 235 mgKOH / g.

[0056] The amount of the alkali-soluble polymer (a) in the UV-ray-sensitive composition (C1) or the visible light-sensitive composition (C2) is typically 30 to 70% by weight, preferably 35 to 65% by weight, and more preferably 40 to 60% by weight, based on the total weight of each composition.

[0057] (Polymerizable compound (b)) The UV radiation-sensitive composition or the visible light-sensitive composition, respectively, comprises a polymerizable compound as component (b) that can undergo free radical-initiated polymerization and / or crosslinking. Such compounds are well known in the art and may hereinafter be referred to as "monomers". The monomer is not particularly limited as long as it has at least one ethylenically unsaturated bond and is a photopolymerizable compound. Any suitable monomer may be used as the sole monomer or in combination with others.

[0058] The polymerizable compound (b) is selected from the group consisting of butyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-propylheptyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, alkoxylated phenol (meth)acrylate, alkoxylated nonylphenol (meth)acrylate, nonylphenol (meth)acrylate, isobornyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, dihydrodicyclopentadienyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, caprolactone (meth)acrylate, 2-phenoxyethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, The (meth)acrylate compound may be selected from the group consisting of acrylate, benzyl (meth)acrylate, monomethoxytri(propylene glycol) mono(meth)acrylate, polypropoxylated propylene glycol mono(meth)acrylate, monomethoxyneopentyl glycol propoxylate mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, acetoacetoxyethyl (meth)acrylate, cyclopentenyloxyethyl (meth)acrylate, 9-anthracenylmethyl (meth)acrylate, 1-pyrenylmethyl (meth)acrylate, lauryl (meth)acrylate, and combinations thereof.

[0059] The polymerizable compound (b) is selected from the group consisting of 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, polybutadiene di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tri(ethylene glycol) di(meth)acrylate, tetra(ethylene glycol) di(meth)acrylate, poly(ethylene glycol) di(meth)acrylate, di(propylene glycol) di(meth)acrylate, tri(propylene glycol) di(meth)acrylate, The di(meth)acrylate compound may be selected from the group consisting of tetra(propylene glycol) di(meth)acrylate, tetra(propylene glycol) di(meth)acrylate, poly(propylene glycol) di(meth)acrylate, glyceryl ethoxylate di(meth)acrylate, glyceryl propoxylate di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol ethoxylate di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, bisphenol A ethoxylate di(meth)acrylate, bisphenol A propoxylate di(meth)acrylate, bisphenol A ethoxylate propoxylate di(meth)acrylate, and combinations thereof.

[0060] The polymerizable compound (b) is selected from the group consisting of trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, trimethylolpropane propoxylate tri(meth)acrylate, glyceryl tri(meth)acrylate, tri(meth)acrylate, glyceryl ethoxylate tri(meth)acrylate, glyceryl propoxylate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ether, The poly(meth)acrylate compound may be selected from the group consisting of pentaerythritol penta(meth)acrylate, pentaerythritol propoxylate tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, di-trimethylolpropane ethoxylate tetra(meth)acrylate, di-trimethylol-propane propoxylate tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethoxylate penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and combinations thereof.

[0061] Preferred polymerizable compounds include polypropoxylated propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, polyethoxylated trimethylolpropane tri(meth)acrylate, and mixtures thereof.

[0062] Other preferred polymerizable compounds include bisphenol A type (meth)acrylates, such as 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypolypropoxy)-phenyl)propane, 2,2-bis(4-((meth)acryloyloxypolybutoxy)phenyl)propane, and 2,2-bis(4-((meth)-acryloyloxypolyethoxypolypropoxy)phenyl)propane. Among them, 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane is preferred from the viewpoint of further improving the resolution and peeling properties.

[0063] In one embodiment, component (b) comprises a polymerizable compound having two or more methacryloyl groups in one molecule.

[0064] In another embodiment, component (b) comprises polyethoxylated bisphenol A di(meth)acrylate, polypropoxylated bisphenol A di(meth)acrylate, polyethoxylated-polypropoxylated bisphenol A di(meth)acrylate, or combinations thereof.

[0065] Commercially available bisphenol A (meth)acrylates include, for example, BPE-200 and BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.), and BPE-900 (manufactured by Sartomer).

[0066] Examples of commercially available polymerizable compounds include polyethoxylated bisphenol A type (meth)acrylates (e.g., "BPE-200" and "BPE-500" manufactured by Shin-Nakamura Chemical Co., Ltd.), or "FA-324M" manufactured by Hitachi Chemical Co., Ltd.; hydroxyl group-containing alkyl acrylates (e.g., "701A" manufactured by Shin-Nakamura Chemical Co., Ltd.); tricyclodecane dimethanol diacrylate (e.g., "A-DCP" manufactured by Shin-Nakamura Chemical Co., Ltd.); polypropylene glycol diacrylate (e.g., "9PG" manufactured by Shin-Nakamura Chemical Co., Ltd.); polyethylene glycol methacrylate (e.g., "14G" manufactured by Shin-Nakamura Chemical Co., Ltd.); 2,2-bis(4-(methacryloxy-polyethoxy)-2,2-dimethyl-2,2-propanediol; Polypropoxy)phenyl)propane (e.g., "FA-3200MY" manufactured by Hitachi Chemical Co., Ltd.); tetramethylolmethane triacrylate (e.g., "A-TMM-3" manufactured by Shin-Nakamura Chemical Co., Ltd.); polyethoxylated trimethylolpropane trimethacrylate (e.g., "TMPT21E", "TMPT30E" manufactured by Hitachi Chemical Co., Ltd.); pentaerythritol triacrylate (e.g., "SR444" manufactured by Sartomer); dipentaerythritol hexaacrylate (e.g., "A-DPH" manufactured by Shin-Nakamura Chemical Co., Ltd.); and polyethoxylated pentaerythritol tetraacrylate (e.g., "ATM-35E" manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0067] The amount of the polymerizable compound (b) in the UV-ray-sensitive composition (C1) or the visible light-sensitive composition (C2) is typically 10 to 70% by weight, preferably 20 to 60% by weight, and more preferably 30 to 50% by weight, based on the total weight of each composition.

[0068] (Photoinitiator (c)) As the component (c), the photoinitiator (c) is not particularly limited and is appropriately selected from conventionally used photoinitiators.

[0069] Examples of such photoinitiators include, but are not limited to, acetophenone compounds such as 2,2-diethoxyacetophenone, 2-methyl-1-[4'-(methylthio)-2-morpholinopropiophenone, 1-hydroxycyclohexyl phenyl ketone, 4-(2-hydroxy-ethoxy)phenyl-2-hydroxy-2-propyl ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether ether, etc. benzoin compounds such as benzoin, benzoin isobutyl ether, and 2,2-dimethoxy-2-phenylacetophenone; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (o-Cl-HABI), 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole (TCDM-HABI), and 2,2'-bis(2 hexaaryl-biimidazole compounds, abbreviated as "HABI", such as 4,4',5,5'-tetraphenyl-2H-1,2'-biimidazole; benzoylphosphine oxide compounds, such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; 1-[4-(phenylthio)phenyl]-1,2-octanedione. These include oxime ester compounds such as 2-(O-benzoyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) (Irgacure OXE02), and 3-cyclopentyl-1-[9-ethyl-6-(2-methyl-benzoyl)-9H-carbazol-3-yl]-1-propanone-1-(O-acetyloxime).

[0070] These photopolymerization initiators may be used alone or in combination of two or more.

[0071] In one embodiment, the photoinitiator (c) comprises a hexaarylbiimidazole compound, a benzoylphosphine oxide compound, an oxime ester compound, or a combination thereof.

[0072] In another embodiment, the photoinitiator (c) includes o-Cl-HABI, TCDM-HABI, and mixtures thereof.

[0073] Suitable photoinitiators are commercially available, for example, o-Cl-HABI and TCDM-HABI can be purchased from Hampford Research Inc.; benzoylphosphine oxide compounds can be purchased from IGM Resins USA Inc.; and oxime ester compounds can be purchased from Changzhou Tronly New Electronic Materials Co., Ltd.

[0074] The amount of photoinitiator (c) in the UV-ray-sensitive composition (C1) or the visible light-sensitive composition (C2) is typically 0.1 to 20% by weight, preferably 0.5 to 10% by weight, and more preferably 1 to 5% by weight, based on the total weight of each composition.

[0075] (UV absorbing sensitizer (d1)) As a sensitizer suitable for use in the UV-ray sensitive composition (C1), the UV-absorbing sensitizer (d1) has a maximum absorption in the UV-ray region, i.e., below 400 nm; preferably, between 300 nm and 400 nm, to provide additional absorption in the UV-ray region.

[0076] Suitable UV absorbing sensitizers (d1) include benzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-dimethoxybenzophenone, (4-(dimethylamino)phenyl)phenylmethanone, (4-(diethylamino)phenyl)-phenylmethanone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone, N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylamino-benzophenone, aromatic ketones such as N, 4-benzoyl-4'-methyl-diphenyl sulfide; acridine compounds such as 9-phenylacridine, and 1,7-bis(9,9'-acridinyl)heptane; aromatic sulfone compounds such as sulfonyldibenzene, 4,4'-sulfonylbis(N,N-dimethyl-benzenamine), 4,4'-sulfonylbis(N,N-diphenylbenzenamine), and 9,9'-(sulfonyldi-4,1-phenylene)bis-9H-carbazole.

[0077] The amount of the UV absorbing sensitizer (d1) in the UV radiation sensitive composition (C1) is 0 to 20 wt %, or 0.01 to 10 wt %, or 0.1 to 5 wt %, based on the total weight of the UV radiation sensitive composition.

[0078] (Visible light absorbing sensitizer (d2)) As a suitable sensitizer for use in the visible light sensitive composition (C2), the visible light absorbing sensitizer (d2) is expected to extend the spectral response of the photoinitiator (c), and preferably with a maximum absorption wavelength in the visible light region of 400 nm to 700 nm.

[0079] Examples of the visible light absorbing sensitizer (d2) include ketones, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbenes, triazines, thiophenes, naphthalimide compounds, bis(p-dialkylaminobenzylidene) ketones, and arylidene aryl ketones.

[0080] Preferred visible light absorbing sensitizers (d2) include 1,3-bis(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)-2-propanone (Bis-Fischer's Base Ketone, BFBK), 3-benzoyl-7-(diethylamino)-2H-1-benzopyran-2-one, 3-benzoyl-7-diethylaminocoumarin, 7-(diethylamino)-3-(7-(diethylamino)-2-oxochroman-3-carbonyl)-2H-chromen-2-one, 3-(2-N-methylbenzimidazolyl)-7-N,N-diethylaminocoumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-(2-benzoxazolyl ... )-7-(diethylamino)coumarin, (E)-1-phenyl-3-(2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)-2-propen-1-one (julolidine chalcone), 4-(dimethylamino)chalcone, (2E,5E)-2,5-bis[4-(dimethylamino)benzylidene]-cyclopentanone, (2E,5E)-2,5-bis[4-(diethylamino)benzylidene]-cyclopentanone, and ketocyanine dyes.

[0081] Suitable visible light absorbing sensitizers (d2) are commercially available, for example, Bis-Fischer's Base Ketone can be purchased from Hampford Research Inc; 3-benzoyl-7-(diethylamino)-2H-1-benzopyran-2-one can be purchased from Changzhou Tronly New Electronic Materials Co., Ltd.

[0082] The amount of the visible light absorbing sensitizer (d2) in the visible light sensitive composition (C2) is 0.01 to 20 wt %, or 0.05 to 10 wt %, or 0.1 to 5 wt %, based on the total weight of the visible light sensitive composition (C2).

[0083] (Other Additives (e)) Other compounds conventionally added to photosensitive compositions may also be present in the UV radiation-sensitive or visible light-sensitive compositions, including hydrogen donors, adhesion modifiers, colorants, leveling agents, plasticizers, surfactants, stabilizers, antioxidants, polymerization inhibitors, crosslinking agents, and the like.

[0084] The hydrogen donor can be added to improve the sensitivity and contrast between the exposed and unexposed areas of the photosensitive composition after exposure to actinic radiation. As long as the hydrogen donor has the above-mentioned properties, the specific chemical species is not particularly limited and can be selected from, but is not limited to, amine compounds, carboxylic acid compounds, mercapto-containing compounds, alcohol compounds, etc.

[0085] The amine compounds include, but are not limited to, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, and n-butylamine; and aromatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethyl-aminobenzoate, 2-ethylhexyl 4-(dimethyl-amino)-benzoate, 2-butoxyethyl 4-(dimethyl-amino)benzoate, 2-dimethylaminoethyl benzoate, N-dimethyl-p-toluidine, 4,4'-bis(dimethyl-amino)benzophenone, and 4,4'-bis(diethyl-amino)benzophenone (Michler's ketone).

[0086] Carboxylic acid compounds include aromatic heteroacetic acids such as, but are not limited to, (phenylthiol)acetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

[0087] Mercapto-containing compounds include, but are not limited to, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, dodecyl mercaptan, octanediol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexa(3-mercaptobutyrate); ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), and the like.

[0088] Alcohol compounds include, but are not limited to, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, neopentyl alcohol, n-hexanol, cyclohexanol, ethylene glycol, 1,2-propanediol, 1,2,3-propanetriol, benzyl alcohol, phenethyl alcohol, and the like.

[0089] The amount of the hydrogen donor may be 0 to 20 parts by weight, preferably 0.01 to 10 parts by weight, in 100 parts by weight of the UV-ray-sensitive composition or the visible light-sensitive composition. When the amount of the hydrogen donor is within the above range, it is advantageous to control the sensitivity of the photosensitive resin composition.

[0090] Adhesion modifiers may be added to improve the adhesion of the coating to the substrate and / or prevent the formation of residues during processing. Suitable adhesion modifiers include heterocyclic chelating moieties such as benzotriazole, 5-chloro-1H-benzotriazole, 1-chloro-1H-benzotriazole, 4- and 5-carboxy-1H-benzotriazole, 1-hydroxy-1H-benzotriazole, 2-mercaptobenzoxazole, 1H-1,2,4-triazole-3-thiol, 5-amino-1,3,4-thiodiazole-2-thiol, 2-mercaptobenzimidazole, and the like. Citric acid is an example of a non-heterocyclic chelating compound that is effective in this way, i.e., to improve the adhesion of the coating and / or prevent the formation of residues.

[0091] Examples of coloring substances include fuchsine, phthalocyanine green, auramine base, paramagienta, leuco crystal violet (LCV), methyl orange, Nile blue 2B, Victoria blue, malachite green chloride salt (Sigma-Aldrich), basic blue 20, diamond green (Hodogaya Chemical Co., Ltd.), and the like.

[0092] Examples of leveling agents include fluorine-based compounds, silicone-based compounds, and acrylic compounds.

[0093] Examples of plasticizers include phthalate esters such as dimethyl phthalate and diethyl phthalate, trimellitate esters such as tris(2-ethylhexyl) trimellitate; aliphatic dibasic acid esters such as dimethyl adipate and dibutyl adipate; orthophosphate esters such as tributyl phosphate and triphenyl phosphate; and acetate esters such as glyceryl triacetate and 2-ethylhexyl acetate.

[0094] Surfactant can be added to improve the coating properties of photosensitive composition.Examples of surfactant include, among others, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, F171, F172 and F173 (available from Dainippon Ink and Chemicals, Japan), FC430 and FC431 (available from Sumitomo 3M Ltd., Japan), KP341 (available from Shin-Etsu Chemical Co., Ltd., Japan).

[0095] Examples of stabilizers include hindered amine-based compounds and benzoate-based compounds. Examples of antioxidants include phenol-based compounds. Examples of polymerization inhibitors include methoquinone, methylhydroquinone, and hydroquinone. Examples of crosslinkers include polyisocyanates and melamine compounds.

[0096] Other additives (e) are generally present in small amounts (ie, less than 10% by weight) so as not to interfere with the functional properties of the photosensitive composition of this invention.

[0097] (Visible light blocking material (f)) Component (f) is a visible light blocking material that can be added to the UV-ray sensitive composition (C1) and absorbs visible light. Visible light absorbing materials include organic materials such as dyes or pigments; inorganic materials such as metal oxide particles, and metal complexes of organic materials. Examples of such visible light absorbing materials include, but are not limited to, those disclosed in DL Jinkerson, (Patent Document 3).

[0098] Suitable visible light absorbing materials include, but are not limited to, methine compounds, ketimide compounds, naphthoyldiamines, nitrodiphenylamine compounds, aminoketone compounds, nitro compounds, anthraquinone compounds, quinoline compounds, benzothiazole compounds, benzimidazole compounds, benzanthracene compounds, such as Eastman Yellow 035-MA (Eastman Chemical); and azo metal complex compounds.

[0099] Examples of metal oxide particles include TiO2, CoO and Fe2O3 nanoparticles. The diameter of the nanoparticles is generally in the range of 20nm to 50nm with visible light absorbing properties.

[0100] Examples of commercially available visible light blocking materials include azo yellow pigments (e.g., Hansa Yellow 10G manufactured by Clariant), naphthol yellow pigments (e.g., Permanent Yellow manufactured by Clariant), benzimidazolone yellow pigments (e.g., CI Yellow 154 manufactured by Arichemie GmbH), azo condensation yellow pigments (e.g., Cromophtal Yellow 3G manufactured by BASF), and the like.

[0101] Other commercially available visible light blocking materials include dyes such as Eusorb UV1990, Eusorb UV-1995, and Eusorb UV-4000, manufactured by Eutec chemical Co., Ltd.; ANSORB-460, ANSORB-475 and ANSORB-930, manufactured by Anchem Technology Corporation.

[0102] The visible light blocking material may contain two or more substances. By adding a plurality of visible light absorbing substances as component (f), the UV ray sensitive composition (C1) is inhibited from photopolymerization by exposure to visible light of 400 nm to 800 nm.

[0103] (UV blocking material (g)) Component (g) is a UV blocking material that absorbs UV radiation and is added to the visible light sensitive composition (C2). For example, the UV blocking material can be tailored to block radiation in the UV region of the electromagnetic spectrum, approximately 200 nm to 400 nm.

[0104] Suitable UV-ray materials (g) include benzophenone compounds, benzotriazole compounds, triazine compounds, compounds with polymerizable moieties, and nanoparticles.

[0105] Examples of benzophenone compounds include, but are not limited to, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-(octyloxy)benzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-,4,4'-dimethoxybenzophenone, and the like.

[0106] Examples of benzotriazole compounds include octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2'-hydroxy-5'-tert-butylphenyl)-benzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octyl-phenyl)- )benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-[2H-benzotriazol-2-yl]-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2'-hydroxy-3',5-di-tert-butylphenyl)benzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)-benzotriazole, and the like.

[0107] Examples of triazine compounds include, but are not limited to, 2-[4-[2-hydroxy-3-tridecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[2-hydroxy-3-didecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-(3-((2-ethylhexyl)oxy)-2-hydroxypropoxy)-phenol, and the like.

[0108] UV radiation blocking materials (g) also include compounds that have polymerizable moieties in their chemical structure, such as vinyl, acrylate, or methacrylate functionality.

[0109] Examples of compounds having a polymerizable moiety include 2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate, 3-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate, 3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate, 3-(5 -chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate, 2-hydroxy-5-methoxy-3-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate, 2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate; and 2-hydroxy-5-methyl-3-(5-(trifluoro 2-(3-(3-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxy-5-methoxyphenyl)-propylthio)ethyl methacrylate, and 3-(4-hydroxy-3-methoxy-5-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)phenyl)propyl methacrylate; 4-allyl- These include, but are not limited to, 2-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-6-methoxyphenol, 4-allyl-2-methoxy-6-(5-(trifluoro-methyl)-2H-benzo[d][1,2,3]triazol-2-yl)phenol, and 3-(4-hydroxy-3-methoxy-5-(5-(trifluoro-methyl)-2H-benzo[d][1,2,3]triazol-2-yl)phenyl)propyl methacrylate.

[0110] Examples of commercially available UV radiation blocking materials include ultraviolet absorbing polymers such as VANARESIN UVA-5080, UVA-7075, UVA-55T, UVA-73T, UVR-8001E, UVR-9001, NEWCOAT UVA-101, NEWCOAT UVA-102, NEWCOAT UVA-103, NEWCOAT UVA-104 manufactured by Shin-Nakamura Chemical Co., Ltd.; and 2,2',4,4'-tetrahydroxybenzophenone manufactured by Everlight.

[0111] The amount of the UV ray blocking material (g) is about 0.01-20.0 wt%, or about 0.05-15 wt%, or about 0.1-10 wt%, based on the total amount of the visible light sensitive composition (C2). When the amount of the component (g) is within this range, it is easy to provide good UV ray blocking ability and resolution and adhesion of the dry film resist in a well-balanced manner.

[0112] (Set of dry films (DF1) and (DF2)) Dry films are generally prepared by coating a photosensitive composition onto a support film to form a photosensitive layer in an uncured state, which is then covered with a protective film when it is stored in roll form. The photosensitive layer may be referred to interchangeably as a "photoresist," "resist," or "dry film resist."

[0113] The transparent conductive substrate of the present invention comprises a first resist layer and a second resist layer, where the first resist layer is composed of a UV-ray sensitive composition, and the second resist layer is composed of a visible light sensitive composition. As a result, a series of dry films DF1 and DF2 are provided, where DF1 is a UV-ray sensitive dry film, and DF2 is a visible light sensitive dry film. The series of dry films (i.e., DF1 and DF2) are suitable for producing the transparent conductive substrate of the present invention, which undergoes a double-sided photolithography process to produce a transparent conductive laminate.

[0114] DF1 includes a support film, a resist layer made of the above-mentioned UV-sensitive composition (C1), and optionally a protective film.DF2 includes a support film, a resist layer made of the above-mentioned visible light-sensitive composition (C2), and optionally a protective film.

[0115] The support film is generally a polymer film, and preferably has high dimensional stability with a transmittance of more than 90% for light in the 350 nm to 420 nm region.

[0116] The support film may be made of polyamide, polyolefin, polyester, vinyl polymer, and cellulose ester. Particularly suitable support films are polymer films made of polyethylene terephthalate, polyethylene, or polypropylene. The thickness of the support film is 1 μm to 100 μm, preferably 5 μm to 50 μm, and more preferably 10 μm to 30 μm.

[0117] The protective film may be selected from the same group of polymer films described above with respect to the support film and may have the same broad range of thicknesses. However, it is preferred that the protective film has a lower adhesion to the resist layer compared to the adhesion of the resist layer to the support film. Particularly suitable protective films are polymer films made of polyethylene, polypropylene, or polyethylene terephthalate. The thickness of the protective film is 1 μm to 100 μm, preferably 5 μm to 50 μm, more preferably 10 μm to 30 μm.

[0118] Examples of commercially available polymer films include the PS series of polyethylene terephthalate films manufactured by Teijin Limited and the FB series of polyethylene terephthalate films manufactured by Toray Industries, Inc.; polyethylene films such as ALPHAN MA-410 and E-200 manufactured by Oji Paper Co., Ltd.; and polypropylene films manufactured by Shin-Etsu Film Co., Ltd.

[0119] When the UV-ray sensitive photosensitive composition or the visible light sensitive composition is in a liquid form with suitable viscosity, it can be directly coated onto a support film to form a corresponding resist layer.Preferably, the UV-ray sensitive composition (C1) and the visible light sensitive composition (C2) are each dissolved in an organic solvent to reduce the viscosity and enable the formation of a respective resist layer with a uniform thickness.

[0120] Examples of suitable solvents include alcohols such as methanol, ethanol, propanol, butanol, etc.; ethers such as tetrahydrofuran; ketones such as acetone and methyl ethyl ketone; glycol ethers such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; aromatic hydrocarbon solvents such as toluene; aprotic polar solvents such as N,N-dimethylformamide; and mixtures thereof. The solvent can be appropriately selected depending on the solubility of the photosensitive composition.

[0121] The method for preparing the UV-ray sensitive composition (C1) and the visible light sensitive composition (C2) according to the present disclosure is not particularly limited, and these compositions can be obtained by mixing the individual components contained in each composition by known methods.

[0122] In addition, filtration may be performed through a filter to remove foreign matter or reduce defects. Any filter may be used without particular limitation as long as it has been conventionally used for filtration or the like.

[0123] In one embodiment, the UV-sensitive dry film (DF1) and the visible light-sensitive dry film (DF2) can be produced by applying a coating solution containing the respective composition to a support film; and drying the resultant to form a resist layer.

[0124] The solid content of the coating solution containing each composition can be appropriately selected depending on the application method and tool. For example, an organic solvent can be used to obtain a solution with a solid content of about 15% by weight to about 60% by weight.

[0125] The coating solution can be applied to the support film by known methods such as roll coating, comma coating, gravure coating, air knife coating, die coating, or bar coating.

[0126] Drying is preferably carried out for about 5 minutes to about 60 minutes at 25° C. to 120° C. The amount of residual solvent in the photosensitive layer after drying is preferably 2% by weight or less.

[0127] The thickness of the dry film (DF1 and DF2) can be appropriately selected depending on the intended use. The thickness of the resist layer after drying is 0.1 μm to 50 μm; or 0.2 μm to 30 μm; or 0.3 μm to 25 μm.

[0128] The shape of the resulting dry film is not particularly limited. The dry film can be in sheet form or can be wound into a roll shape around a core. When the dry film is wound into a roll shape, it is preferred that the support film faces outward.

[0129] The series of dry films (DF1 and DF2) according to this embodiment can be used, for example, in the method for manufacturing a transparent conductive substrate as described below.

[0130] (Method for manufacturing a transparent conductive substrate) The UV radiation sensitive composition (C1) and the visible light sensitive composition (C2) as well as the series of dry films (DF1 and DF2) described previously in this invention can be used to form a transparent conductive substrate.

[0131] In one embodiment, the transparent conductive substrate 100 of the present invention comprises: (i) providing a transparent core; (ii) forming a first transparent conductive layer on one surface of the transparent core; (iii) forming a second transparent conductive layer on an opposite surface of the transparent core; (iv) applying a UV-ray sensitive composition (C1) onto the first transparent conductive layer to form a first resist layer; (v) applying a visible light sensitive composition (C2) onto the second transparent conductive layer to form a second resist layer; The present invention is produced by a method comprising the steps of:

[0132] As previously mentioned, the first conductive layer 21 and the second transparent conductive layer 22 of the transparent conductive substrate of the present invention (see FIG. 1 ) may be formed by applying a dispersion containing a conductive material onto one or both surfaces of the transparent core 10 by spin coating, dipping, or chemical vapor deposition (CVD).

[0133] The formation of the first resist layer 31 or the second resist layer 32 may be carried out by coating a UV-ray sensitive composition (C1) or a visible light sensitive composition (C2) on the surface of the first transparent conductive layer 21 or the second transparent conductive layer 22, respectively, in a suitable solvent as previously described.

[0134] Alternatively, the first or second resist layer may be formed by laminating a series of dry films (i.e., DF1 and DF2) onto the respective transparent conductive layers. If a cover sheet is present in the series of dry films, it may be removed and the uncovered surface of the resist layer is laminated onto the previously cleaned surface of the transparent conductive layer using heat and / or pressure, for example, with a conventional hot roll lamination device. Lamination parameters including temperature, pressure, and duration may be appropriately selected as needed by one skilled in the art.

[0135] It should be noted here that after laminating DF1 and DF2, the resulting transparent conductive substrate contains two additional polymer films derived from the support films of dry films DF1 and DF2. As shown in FIG. 2, the transparent conductive substrate 200 has a structure in the order of a first polymer film 41, a first resist layer 31, a first transparent conductive layer 21, a transparent core 10, a second transparent conductive layer 22, a second resist layer 32, and a second polymer film 42.

[0136] The polymer films 41 and 42 act as protective sheets and the transparent conductive substrate 200 can be exposed to light through the polymer films. In some cases, the polymer films can be removed prior to irradiation to improve resolution and other such properties.

[0137] In one embodiment, the transparent conductive substrate 200 of the present invention comprises: (I) providing a transparent core and a series of dry films consisting of a UV light sensitive dry film (DF1) and a visible light sensitive dry film (DF2); (II) forming a first transparent conductive layer on one surface of the transparent core; (III) forming a second transparent conductive layer on an opposite surface of the transparent core; (IV) optionally, if present, removing the first and second protective films from the sequence of dry films; (V) simultaneously laminating a UV radiation sensitive dry film onto the first transparent conductive layer and a visible light sensitive dry film onto the second transparent conductive layer; Methods including And, The UV-sensitive dry film (DF1) includes a support film, a resist layer composed of a UV-sensitive composition (C1), and optionally a protective film; The visible light sensitive dry film (DF2) comprises a support film, a resist layer composed of a visible light sensitive composition (C2), and optionally a protective film. It is produced by the method.

[0138] Method for producing transparent conductive laminates The present invention also provides a double-sided photolithographic method for producing a transparent conductive laminate, comprising the steps of: (A) providing a transparent conductive substrate of the present invention; (B) simultaneously exposing the first resist layer to a first light source and the second resist layer to a second light source; At the same time, (C) developing the first resist pattern and the second resist pattern by removing the unexposed portions of each resist layer; (D) simultaneously etching portions of the first transparent conductive layer and the second transparent conductive layer that are not protected by their respective resist patterns; (E) simultaneously stripping the first resist pattern and the second resist pattern to provide a transparent conductive laminate; Where: The transparent conductive laminate includes a first conductive circuit and a second conductive circuit on each side of a transparent core, the design patterns of the first conductive circuit and the second conductive circuit being different from each other; the first light source and the second light source are disposed on opposite sides of a transparent conductive substrate; a first light source irradiates light at a wavelength of less than 400 nm and at a target exposure energy for the first resist layer, such that the second resist layer is substantially free of being patterned by the first light source; The second light source irradiates light at a wavelength of 400 nm to 800 nm and at a target exposure energy for patterning the second resist layer, such that the first resist layer is substantially free of patterning by the light irradiated by the second light source. A method is provided.

[0139] FIG. 3 illustrates the steps of the double-sided photolithography method of the present invention for producing a transparent conductive laminate.

[0140] The first step of the method of the present invention is (A) to provide a transparent conductive substrate of the present invention, which can be a transparent conductive substrate 100 as shown in FIG. 1 or a transparent conductive substrate 200 as shown in FIG. 2.

[0141] Referring to FIG. 3A, the transparent conductive substrate of the present invention is placed between two light sources disposed on opposite sides of the transparent conductive substrate, such that the first resist layer 31 faces a first light source 110 and the second resist layer 32 faces a second light source 120.

[0142] The second step in the method of the present invention is (B) simultaneously exposing the first resist layer to a first light source and the second resist layer to a second light source (see FIG. 3A).

[0143] Examples of exposure methods include a method of irradiating light imagewise through a negative or positive pattern (i.e., a photomask), which is called a mask exposure method. Alternatively, a method of irradiating light imagewise by a direct writing exposure method such as an LDI (laser direct imaging) exposure method or a DLP (digital light processing) exposure method may be used.

[0144] For example, for a first resist layer that is a UV-ray sensitive photoresist, a 355 nm and 375 nm laser light LDI machine can be selected; for a second resist layer that is a visible light sensitive photoresist, a 405 nm and 438 nm laser light LDI machine can be selected.

[0145] Any convenient source of actinic radiation that provides wavelengths in the region of the spectrum that overlaps with the absorption bands of the photoinitiator and / or sensitizer may be used to activate the photopolymerization reaction. Conventional light sources include gas lasers such as carbon arc lamps, mercury vapor arc lamps, ultra-high pressure mercury lamps, xenon lamps, or argon lasers; solid-state lasers such as YAG lasers; semiconductor lasers; ultraviolet light such as gallium nitride-based violet lasers; and lamps that efficiently emit visible light.

[0146] During the simultaneous exposure step (B), the first resist layer is irradiated by a first source of UV light (less than 400 nm) and the second resist layer is irradiated by a second source of visible light (400 nm to 800 nm). Because the transparent conductive substrate is "transparent," there is some incident light passing through the multiple layers and reaching the resist layer on the opposite side.

[0147] One determining factor of the method is the reliance on the first and second resist layers each having different sensitivity to different wavelengths of radiation. Another determining factor is the ability of the dry film resist to block the actinic radiation of a particular resist layer from passing through and reaching the resist layer on the opposite side of the transparent conductive substrate.

[0148] For example, the first resist layer 31, composed of a UV-ray sensitive composition (C1), is photocured by exposure to UV-rays at wavelengths below 400 nm, preferably at 365 nm. Because the UV-ray sensitive composition (C1) contains a UV-absorbing sensitizer (d1) and / or a visible light blocking substance (f), the first resist layer 31 is insensitive to (or less sensitive to) the incident visible light used to expose the second resist layer. Similarly, the second resist layer is photocured by exposure to visible light at wavelengths between 400 nm and 800 nm, and because of the presence of the visible light absorbing sensitizer (d2) and the UV-ray blocking substance (g) in the visible light sensitive composition (C2), the second resist is insensitive to incident light below 400 nm. As a result, the method can imagewise expose the first resist layer and the second resist layer simultaneously to form different or unique resist patterns on both sides of a transparent conductive substrate.

[0149] The third step of the method of the present invention is (C) simultaneously developing the first resist pattern 33 and the second resist pattern 34 by removing the unexposed parts of each resist layer (see FIG. 3B).

[0150] When the polymer film remains on the first and second resist layers, the support film is peeled off, and then the unexposed areas of each resist layer are removed (developed). Examples of development processes include wet development and dry development, with wet development being widely used.

[0151] The developing solution (i.e., the developer) is generally an aqueous solution of a water-soluble base at 0.01% to 5% by weight. Suitable water-soluble bases include alkali metal hydroxides such as lithium, sodium, and potassium hydroxide; base-reactive alkali metal salts of weak acids such as lithium, sodium, and potassium carbonate and bicarbonate; ammonium hydroxide and tetra-substituted ammonium hydroxides such as tetramethylammonium and tetraphenylammonium hydroxide; sulfonium salts including hydroxides, carbonates, bicarbonates, and sulfides; alkali metal phosphates and pyrophosphates such as sodium and potassium triphosphates and pyrophosphates; tetra-substituted phosphonium, arsonium, and stibonium hydroxides such as tetramethylphosphonium hydroxide. A preferred developer is an aqueous solution of 0.1 to 3% by weight of sodium carbonate.

[0152] The developer may also contain surfactants, however the total organic content should be less than 10% by weight, preferably less than 5% by weight.

[0153] Resist pattern development can be carried out on the first and second resist layers simultaneously as a batch or continuous process using any conventional technique, such as immersion or spraying. Development can be carried out at room temperature or heated to a temperature of up to about 50° C. Many commercial processing equipment are available for development.

[0154] The fourth step of the method of the present invention is (D) etching the portions of the first transparent conductive layer and the second transparent conductive layer that are not protected by their respective resist patterns (see FIG. 3C).

[0155] The etching method can be appropriately selected according to the constituent material of the transparent conductive layer to be removed. The etching method can be performed on the first transparent conductive layer and the second transparent conductive layer simultaneously.

[0156] Examples of etching solutions include solutions for etching silver-containing conductive layers, in which the content of nitrate ions is about 16.0% by weight to about 35.0% by weight with respect to the total amount of the etching solution.

[0157] The ion source of the nitrate ion is not particularly limited as long as it can be dissolved in water to generate nitrate ion. Examples of nitrate ion sources include nitric acid, potassium nitrate, sodium nitrate, ammonium nitrate, uranyl nitrate, calcium nitrate, silver nitrate, iron (II) nitrate, iron (III) nitrate, and lead (II) nitrate, barium nitrate, cobalt (II) nitrate, bismuth (III) nitrate, strontium nitrate, magnesium nitrate, calcium nitrate, diammonium cerium (IV) nitrate, palladium (II) nitrate, copper (II) nitrate, cadmium nitrate, thallium (III) nitrate, cerium (III) nitrate, zinc nitrate, nickel (II), zirconyl nitrate, aluminum nitrate, lithium nitrate, mercury (II) nitrate, cesium nitrate, gadolinium (III) nitrate, erbium (III) nitrate, europium (III) nitrate, lutetium (III) nitrate, indium (III) nitrate, yttrium (III) nitrate, gallium nitrate, samarium (III) nitrate, or ytterbium (III) nitrate.

[0158] From the viewpoint of increasing the etching rate more easily, the ion source of the nitrate ion preferably contains one or more selected from the group consisting of nitric acid, iron (II) nitrate, and iron (III) nitrate. Iron (III) functions as an effective catalyst for nitric acid to oxidize silver from the viewpoint of oxidation-reduction potential. Therefore, from the viewpoint of increasing the etching rate more easily, the ion source of the nitrate ion more preferably contains iron (III) nitrate.

[0159] The fifth step of the method of the present invention is (E) simultaneously stripping the first resist pattern and the second resist pattern to provide a transparent conductive laminate having two conductive circuits 23 and 24 on both sides of the transparent core 10 (see FIG. 3D).

[0160] Once the first resist pattern and the second resist pattern have performed their functions, the resist patterns can then be generally removed by an aqueous stripping solution, which may contain an organic amine or a solvent to improve the stripping speed or to minimize metal attack or contamination. The aqueous stripping solution typically has a stronger alkalinity than that of the aqueous developer used to develop the resist pattern. The aqueous stripping solution can be an aqueous solution of 1-10% by weight of sodium hydroxide or potassium hydroxide.

[0161] Examples of resist pattern stripping methods include dipping and spraying, which may be used alone or in combination. The stripping method may be performed on the first transparent conductive layer and the second transparent conductive layer at the same time.

[0162] Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following examples are therefore to be construed as merely illustrative and not limiting of the disclosure in any way. EXAMPLES

[0163] (raw materials) (Alkali-soluble copolymer (a):) A-1: A copolymer composed of methyl methacrylate / benzyl methacrylate / methacrylic acid / styrene (32 / 18 / 25 / 25), with a Mw of 55,000, a dispersity of 2.2 and an acid value of 162.8 mg KOH / g. (Polymerizable compound (b)) B-1: Polyethoxylated bisphenol A dimethacrylate, total 17EO, CAS number 41637-38-1, purchased from Sartomer, trade name: BPE900. B-2: Trimethylolpropane trimethacrylate, CAS number 3290-92-4, purchased from Sartomer, trade name: SR350NS. (Photoinitiator (c)) C-1: o-Cl-HABI, 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenyl-2H-imidazol-2-yl]-4,5-diphenyl-1H-imidazole, CAS number 7189-82-4, purchased from Hampford Research Inc. C-2: TCDM-HABI, 2,2′,4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4′,5′-diphenyl-1,1′-bi-1H-imidazole, CAS number 100486-97-3, purchased from Hampford Research Inc. C-3: OMNIRAD 369, 2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-2-(phenylmethyl)-1-butanone, CAS number 119313-12-1, purchased from IGM resins. C-4: 3-Cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-propanone-1-(O-acetyloxime), CAS number 1227375-90-7, purchased from Changzhou Tronly New Electronic Materials Co., Ltd., product name: TR-PBG-304. (Sensitizer (d)) D1-1: 4,4′-bis(diethylamino)benzophenone, CAS number 90-93-7, purchased from Sigma-Aldrich. D1-2: 4-(Dimethylamino)benzophenone, CAS number 530-44-9, purchased from Sigma-Aldrich. D2-1: BFBK, 1,3-bis(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)-2-propanone, CAS number 24293-93-4, purchased from Hampford Research Inc. D2-2: 3-benzoyl-7-(diethylamino)-2H-benzopyran-2-one, CAS number 77016-78-5, purchased from Changzhou Tronly New Electronic Materials Co., Ltd., product name: TR-PSS-202. (Other Additives (e)) E-1: LCV, Leuco Crystal Violet, CAS number 603-48-5, purchased from Changzhou Tronly New Electronic Materials Co, Ltd., product name: TR-LCV. E-2: 5-Carboxy-1H-benzotriazole, CAS number 60932-58-3, purchased from PMC Specialties Group USA. E-3: 5-chloro-1H-benzotriazole, CAS number 94-97-3, purchased from Sigma-Aldrich. E-4: Malachite green, chloride salt, CAS number 569-64-2, purchased from Sigma-Aldrich. E-5: 4-tert-Butylcatechol, CAS number 98-29-3, purchased from Sigma-Aldrich. (Visible light blocking material (f)) F-1: Eusorb UV-1995, peak absorption at 431 nm (0.2 wt % doped in PMMA polymer and coated on 25 mm film), purchased from Eutec Chemical Co., Ltd. (UV blocking material (g)) G-1: 2,2',4,4'-tetrahydroxybenzophenone, CAS number 131-55-5, peak absorption at 360 nm (0.2 wt % doped in PMMA polymer and coated on 25 mm film), purchased from Everlight Chemical, product name: Eversorb 51.

[0164] (Preparation of dry film samples (M1 to M11)) Photosensitive compositions for forming dry film samples were prepared by weighing each ingredient in parts by weight as listed in Table 1, and then adding the ingredients to a solvent mixture of acetone and methanol (90:10) to form a coating solution with a solid content of about 30%. The coating solution was cast onto a polyethylene terephthalate (PET) film (i.e., a 16 μm thick support film, manufactured by Toray Industries, Inc.) and dried at room temperature to form a dry film sample containing a resist layer of about 15 μm thickness on the PET film.

[0165] [Table 1]

[0166] (Exposure Energy Evaluation) To evaluate the exposure sensitivity, specimens containing each of the dry film samples M1 to M11 were prepared. 2 Dry film samples (M1-M11) were prepared by laminating them onto a PET film (16 μm thick, manufactured by Toray Industries, Inc.) at 120 °C using a hot roll lamination machine (HRL-24, DuPont Co., Wilmington, Del.) under a press pressure of 1000 and a speed of 2 m / min, and then cooled to room temperature for 1 h to obtain specimens for exposure energy evaluation. Each specimen was cut into a square piece (size: 15 × 15 cm) with a structure of PET film (16 μm) / resist layer (15 μm) / PET film (16 μm). 2 ) PET film (16 μm) / Resist layer (15 μm) / PET film (16 μm).

[0167] Each specimen was irradiated by using an MA8 contact aligner (manufactured by SUSS MicroTech) equipped with a high pressure mercury lamp and a photomask that was either a narrow band-pass filter for exposure in the range of 355-390 nm (UV radiation) or a long-pass filter for exposure above 400 nm (visible light). A step wedge (41 steps, manufactured by Stouffer) was then placed on the PET film and exposed at a preset exposure energy (e.g., 100, 150, 1000 mJ / cm). 2 The specimen was irradiated at 1000 x g for 1 h.

[0168] After exposure and >15 min at room temperature, the PET film was peeled off. The specimens were developed by spraying with 1% aqueous sodium carbonate at a pressure of 0.2 MPa at 30° C. for a duration that was twice the development time. After rinsing with deionized water and drying, the number of steps resulting from the exposure energy retained on the specimen compared to the Stouffer 41 Step Wedge was recorded. The exposure energy (mJ) required to obtain 12 steps retained on the Stouffer 41 Step Wedge for each of the dry film resists (E SST12 ) are listed in Table 2. A higher exposure energy to result in the same number of steps being retained meant that the resist layer had a lower sensitivity at the selected exposure wavelength.

[0169] (Trigger energy calculation) The exposure energy (E) of each dry film sample to obtain a 0-step retention on a Stouffer 41 Step Wedge was SST0 ) to trigger energy (E SST0 ) The trigger energy can be calculated by the following equation: E SST0 =E SST12 / 4 (equation 1)

[0170] Calculated E for dry film samples M1–M11 SST0 The data are listed in Table 2.

[0171] (Measurement of dry film resist transmittance) The transmittance of each dry film sample was measured using a Lambda 35-UV / VIS spectrometer (manufactured by Perlin Elmer. Measurement conditions: wavelength range: 200 nm to 800 nm, scanning speed: 300 nm / min, scanning interval: 0.50 nm). A baseline measurement was performed on a 16 μm thick PET film that was used as a support film for the dry film samples. The transmittance at 365 nm and 405 nm was recorded and listed in Table 2.

[0172] (Calculation of Incident Exposure Energy) As previously discussed and with reference to FIG. 3A, the double-sided photolithography method of the present invention uses two light sources positioned on opposite sides of a transparent conductive substrate. The first resist (DF1) is SST12 Assume that the sample is irradiated by a first source of UV light (e.g., at 365 nm) with an exposure energy of 365 ) can reach the second resist (DF2), and the transmittance at 365 nm of DF1 (T 365 ) and exposure energy (E SST12 ) is calculated.

[0173] Similarly, E SST12 For a second resist (DF2) that is irradiated by a second source of visible light (e.g., at 405 nm) with an exposure energy of 405 ) can reach the first resist (DF1), and the transmittance at 405 nm of DF2 (T 405 ) and exposure energy at 405 nm (E SST12 ) for each dry film sample M1 to M11. 365 ) and incident visible light (Inc.E 405 The calculated exposure energies for each are listed in Table 2.

[0174] (Resolution evaluation of dry film samples M1 to M11) The resolution of dry film samples M1-M11 was evaluated for laminates containing the specified dry film samples and a transparent conductive base. The transparent conductive base consisted of a PET film (i.e., transparent core 10, size: 15 cm x 15 cm x 50 mm) coated with a thin layer of silver nanowires (i.e., first and second transparent conductive layers 21 and 22) on each side of the PET film. The dry film samples were placed on the transparent conductive base to obtain preforms.

[0175] Structure: A preform having [dry film sample / AgNW / PET / AgNW] was placed on a 5 kg / cm 2 The laminate was laminated at 120° C. using a hot roll laminator (HRL-24, DuPont Co., Wilmington, Del.) under a press pressure of 1000 μm and a speed of 2 m / min, and then cooled to room temperature for 15 min.

[0176] The resulting laminate was exposed to 12 steps on a Stouffer 41 Step Wedge using a line mask (chrome glass mask) with a line / space ratio of exposed to unexposed areas of 1:1 at 1000 nm (E SST12 ) for 100 s. The line widths ranged from 5 μm to 30 μm. Development was performed for twice the minimum development time, and the minimum mask line width of the hardened photoresist lines formed was usually taken as the resolution (in μm) and classified as follows: ◎: The resolution is 10 μm or less. A: The resolution is 10 μm to 15 μm. ×: The resolution is 15 μm to 30 μm.

[0177] The resolution of each dry film sample is shown in Table 2.

[0178] [Table 2]

[0179] (Preparation of Transparent Conductive Substrate of Example 1) Dry film samples M2 and M10 were then placed on both sides of a transparent conductive base as DF1 and DF2, respectively, according to Table 3. The transparent conductive base consisted of a PET film (i.e., transparent core 10, size: 15 cm × 15 cm × 50 mm) coated with a thin layer of silver nanowires (i.e., first and second transparent conductive layers 21 and 22) on each side of the PET film.

[0180] The stacked preforms with the structure of PET / M2 / AgNW / PET / AgNW / M10 / PET were subjected to a 5 kg / cm 2 The laminate was laminated at 120° C. using a hot roll laminator (HRL-24, DuPont Co., Wilmington, Del.) under a pressing pressure of 1000 μm and a speed of 2 m / min, and then cooled to room temperature for 1 hour to obtain the transparent conductive substrate of Example 1.

[0181] (Preparation of Transparent Conductive Substrates of Examples 2 to 8 and Comparative Examples 1 to 7) All Examples (E2-E8) and Comparative Examples (CE1-CE7) were prepared by the same procedure as described above for Example 1. The set of dry film samples used in each Example (E2-E8) and Comparative Example are listed in Table 3.

[0182] (Performance of Examples (E1 to E8) and Comparative Examples (CE1 to CE7)) The performance of the transparent conductive substrates containing a series of designations DF1 and DF2 was evaluated after being subjected to a double-sided photolithography process. The prepared transparent conductive substrates of Examples 1-8 and Comparative Examples CE1-CE7 with the structure of [PET / first resist] / AgNW / PET / AgNW / [second resist / PET] were evaluated by patterning with incident light exposure.

[0183] The transparent conductive substrate was exposed by a line mask (chrome glass mask) with a L / S=15mm / 15mm parallel line pattern. The first resist layer 31 was irradiated by a high pressure mercury lamp and with a photomask of a horizontal line pattern for exposure in the range of 355-390nm (UV rays); the second resist layer 32 was irradiated by a high pressure mercury lamp and with a photomask of a vertical line pattern for exposure with visible rays at wavelengths of 400nm or more.

[0184] After development, the patterns on both surfaces of the resulting transparent conductive laminate were visually checked by optical microscopy. The pattern shape on one surface was reflected in the pattern shape on the other surface and evaluated and recorded in Table 3.

[0185] To avoid photocuring of DF2 by incident UV light at 365 nm, a suitable DF2 should have a trigger energy (E SST0 To avoid photocuring of DF1 by incident visible light at 405 nm, a suitable DF1 must have an incident exposure energy (Inc.E 405 ) at least higher than the trigger energy at 405 nm (E SST0 For example, if dry film M3 is used as DF1, potentially suitable dry film samples to be used as DF2 include M8 through M11 according to Table 3.

[0186] The imaging performance of the transparent conductive substrate was evaluated by the amount of residual resist left on the treated transparent conductive substrate after development and is recorded in Table 3.

[0187] The imaging performance of the transparent conductive substrates was categorized as follows: ◎: The intersection area between the horizontal and vertical lines did not show any resist residue (see FIG. 4A) ○: The intersection area between the horizontal and vertical lines showed slight resist residue (see FIG. 4B) ×: The intersection area between the horizontal and vertical lines showed significant resist patterns (see FIG. 4C)

[0188] [Table 3]

[0189] From the results listed in Table 3, the following is evident:

[0190] The transparent conductive substrates of Examples E1-E8 demonstrated good to excellent imaging performance compared to those of Comparative Examples (CE1-CE7) as assessed by the resulting clean resist patterns on both sides of each transparent conductive substrate after peeling. In other words, there is no unexpected polymerization of the resist layer caused by the incident light from the opposite light source.

[0191] In order for the first resist layer and the second resist layer to be photocured by light of different wavelength regions (i.e., UV light or visible light), a suitable photosensitive composition must have an initiator and / or sensitizer designed to absorb either UV light or visible light. If a transparent conductive substrate has resist layers on both sides that are the same, it is expected that by using the double-sided lithography method of the present invention, the resulting transparent conductive laminate will show unacceptable image performance. The above statement is supported by the results found for CE1 and CE2.

[0192] Considering the data for CE1 in Table 3, the incident light energy (Inc. E) from DF2, which is dry film M1, to DF1 405 ) is the visible light trigger energy (E at 405 nm) of dry film M1 as DF1 SST0 ) (i.e., 148 mJ), which is much higher than the incident light energy (Inc. E) from DF1, which is the dry film M1, to DF2. 365 ) is the UV trigger energy (E at 365 nm) of the dry film M1 as DF2SST0 ) (i.e., 39 mJ). Therefore, both the first resist layer and the second resist layer were inevitably patterned by the incident light transmitted through the transparent core from the opposite side.

[0193] Comparing E1 (i.e., composed of dry films M2 / M10) and CE7 (i.e., composed of dry films M1 / M10), E1 used dry film M2 as the first resist layer, while CE7 used dry film M1 as the first resist layer. Although both dry films M1 and M2 contain different sensitizers, they have similar E SST12 (155 mJ vs. 185 mJ). However, the respective trigger energies (E SST0 The first resist layer comprised of M2 in E1 was not patterned by the incident visible light energy (i.e., 226 mJ) that passed through the same second resist layer comprised of dry film M10 because dry film M2 has a lower visible light sensitivity than that of dry film M1, as determined by the incident visible light energy (i.e., 267 mJ for M2 and 148 mJ for M1) that passed through the same second resist layer comprised of dry film M10.

[0194] Comparing E7 (M7 / M10) and E1 (M2 / M10), the addition of visible light blocking material (f) in dry film M7 significantly reduced the E at 405 nm. SST0 This seemingly reduced the sensitivity of the M7 to incident visible light as judged by the IR (283 mJ for M7 vs. 267 mJ for M2).

[0195] While the present invention has been illustrated and described in exemplary embodiments, it is not intended to be limited to the details shown, since various modifications and substitutions are possible without departing from the spirit of the invention. Accordingly, modifications and equivalents of the invention disclosed herein will occur to those skilled in the art using no more than routine experimentation, and all such modifications and equivalents are deemed to be within the spirit and scope of the invention as defined by the following claims. [Explanation of symbols]

[0196] 10 Transparent Core 21 First transparent conductive layer 22 Second transparent conductive layer 23 Conductive Circuit 24 Conductive Circuit 31 First resist layer 32 Second resist layer 33 First resist pattern 34 Second resist pattern 41 First polymer film 42 Second polymer film 100 Transparent conductive substrate 110 First Light Source 120 Second Light Source 200 Transparent conductive substrate

Claims

1. A transparent conductive substrate for manufacturing a transparent conductive laminate, comprising a first resist layer, a first transparent conductive layer, a transparent core, a second transparent conductive layer, and a second resist layer in this order, The transparent conductive substrate has a total transmittance of 60% or more in the range of 400 nm to 800 nm (T ４００～８００ ) has; The first resist layer is composed of a UV-sensitive composition; The second resist layer is composed of a visible light-sensitive composition; The UV-sensitive composition undergoes photopolymerization by exposure to light with a wavelength of less than 400 nm; The visible light-sensitive composition undergoes photopolymerization by exposure to light in the wavelength range of 400 nm to 800 nm. A transparent conductive substrate.

2. The UV-sensitive composition is (a) 30 to 70% by weight of an alkali-soluble copolymer; (b) 10 to 70% by weight of a polymerizable compound having an ethylenically unsaturated double bond; (c) 0.1 to 20% by weight of a photoinitiator; (d1) 0 to 20% by weight of a UV-absorbing sensitizer having maximum absorption in the UV region; (e) with 0 to 20% by weight of other additives; (f) 0 to 20% by weight of a visible light blocking material that absorbs incident visible light energy and A transparent conductive substrate according to claim 1, including the above.

3. The visible light-sensitive composition is (a) 30 to 70% by weight of an alkali-soluble copolymer; (b) 10 to 70% by weight of a polymerizable compound having an ethylenically unsaturated double bond; (c) 0.1 to 20% by weight of a photoinitiator; (d2) 0.01 to 20% by weight of a visible light absorbing sensitizer having maximum absorption in the visible light region; (e) with 0 to 20% by weight of other additives; (g) 0.01 to 20% by weight of a UV-blocking material that absorbs incident UV energy. A transparent conductive substrate according to claim 1, including the above.

4. The transparent conductive substrate according to claim 1, wherein the transparent core is a sheet of glass, flexible glass, or quartz; or a polymer film composed of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, cellulose acetate, polyethylene, polypropylene, cyclic polyolefin, poly(meth)acrylate ester, polyacrylate, polyamide, polyimide, polycarbonate, poly(ethersulfone), polysulfone, or a combination thereof.

5. The transparent conductive substrate according to claim 1, wherein each of the first transparent conductive layer and the second transparent conductive layer independently contains a conductive material selected from indium tin oxide, indium zinc oxide, indium gallium zinc oxide; carbon nanotubes; and copper, silver, platinum, or gold nanowires.

6. The transparent conductive substrate according to claim 1, wherein the transparent core has a thickness of 1 μm to 200 μm; each of the first transparent conductive layer and the second transparent conductive layer independently has a thickness of 0.001 μm to 10 μm; and each of the first resist layer and the second resist layer independently has a thickness of 0.1 μm to 50 μm.

7. A transparent conductive substrate according to claim 1, further comprising a first polymer film in contact with the first resist layer and a second polymer film in contact with the second resist layer, wherein the first polymer film and the second polymer film are each independently composed of polyethylene terephthalate, polyethylene, or polypropylene; and each independently has a thickness of 1 μm to 100 μm.

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