JP2022184720A - Manufacturing method of substrate having conductive pattern, manufacturing method of electronic device, substrate having conductive pattern, and protective film for metal nano substance - Google Patents

Abstract

To provide a manufacturing method of a substrate having a conductive pattern excellent in dimensional stability of the conductive pattern after electric conduction, a manufacturing method of an electronic device, and the substrate having the conductive pattern or a protective film for a metal nano substance.SOLUTION: A manufacturing method of a substrate having a conductive pattern comprises steps of: forming a conductive layer containing a metal nano substrate and first resin 1 on the substrate; forming a resin layer containing second resin on the conductive layer; forming a photosensitive resin layer 17 on the resin layer; obtaining a resin pattern of the photosensitive resin layer by light exposure and development processing to the photosensitive resin layer; removing the metal nano substrate in the conductive layer by etching to form the conductive pattern; and softening or swelling at least one of the first resin and the second resin.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present disclosure relates to a method for manufacturing a substrate having a conductive pattern, a method for manufacturing an electronic device, a substrate having a conductive pattern, and a protective film for a metal nanobody.

In a display device with a touch panel such as a capacitive input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.), the electrode pattern corresponding to the sensor in the visible part, the wiring of the peripheral wiring part and the lead-out wiring part A conductive pattern such as is provided inside the touch panel.
Generally, the formation of a patterned layer requires a small number of steps to obtain the required pattern shape. In contrast, a method of developing after exposure through a mask having a desired pattern is widely used.

Conventionally, printed conductive patterns have been widely used in various fields as various sensors such as pressure sensors and biosensors, printed circuit boards, solar cells, capacitors, electromagnetic wave shields, touch panels, antennas, and the like.

Moreover, as a conventional method for forming a conductive pattern, the methods described in Patent Documents 1 and 2 are known.
Patent Document 1 discloses a film-like transparent substrate having a first surface and a second surface opposite to the first surface, metal nanowires, and a transparent binder containing a water-repellent additive, a transparent conductive film formed on at least one of the first surface and the second surface of the transparent base material, and a part of the metal nanowires are exposed on the surface of the transparent conductive film, and the transparent A transparent conductive film-attached film is described in which the contact angle of the surface of the conductive film is 80 degrees or more and 125 degrees or less.
Moreover, Patent Document 2 describes a method of etching a metal nanowire layer to form a conductive pattern.

WO2016/051695 Taiwan Patent Application Publication No. 2016-29992

A problem to be solved by an embodiment of the present invention is to provide a method for manufacturing a substrate having a conductive pattern that exhibits excellent dimensional stability after energization.
A problem to be solved by another embodiment of the present invention is to provide a method for manufacturing an electronic device having a substrate having a conductive pattern obtained by the method for manufacturing a substrate having a conductive pattern.
A problem to be solved by still another embodiment of the present invention is to provide a substrate or a protective film for a metal nano-body having a conductive pattern with excellent dimensional stability of the conductive pattern after energization.

Means for solving the above problems include the following aspects.
<1> Step 1a of forming a conductive layer a containing a metal nano-body and a resin 1 on a substrate, Step 1b forming a resin layer b containing a resin 2 on the conductive layer a, on the resin layer b , Step 2a of forming a photosensitive resin layer c, Step 3 of obtaining a resin pattern c′ of the photosensitive resin layer by exposing and developing the photosensitive resin layer c, Etching the metal in the conductive layer a A method for producing a substrate having a conductive pattern, comprising a step 4 of removing nano bodies to form a conductive pattern d, and a step 5a of softening or swelling at least one of the resin 1 and the resin 2.
<2> Step 1a of forming a conductive layer a containing a metal nano-body and resin 1 on a substrate, Step 2b of forming a photosensitive resin layer c on the conductive layer a, for the photosensitive resin layer c , step 3 of obtaining a resin pattern c′ of the photosensitive resin layer by exposure and development, step 4 of removing metal nano bodies in the conductive layer a by etching to form a conductive pattern d, and the resin 1 A method of manufacturing a substrate having a conductive pattern, including a step 5b of softening or swelling the .
<3> At least one surface of the substrate having the obtained conductive pattern has a first section in which the conductive pattern d is formed and a second section in which the conductive pattern d is not formed, <1>, wherein the area where voids are observed when the second section is observed with a scanning electron microscope from the thickness direction of the substrate is 10% or less of the total area of the second section, or A method for producing a substrate having a conductive pattern according to <2>.
<4> The area where voids are observed when the second section is observed with a scanning electron microscope from the thickness direction of the substrate is 8% or less of the total area of the second section. 3>, a method for manufacturing a substrate having a conductive pattern.
<5> The area where voids are observed when the second section is observed with a scanning electron microscope from the thickness direction of the substrate is 5% or less of the total area of the second section. 4>, a method for manufacturing a substrate having a conductive pattern.
<6> The method for producing a substrate having a conductive pattern according to any one of <1> to <5>, wherein the conductive layer a has a transmittance of 70% or more for light with a wavelength of 380 nm to 780 nm.
<7> The method for producing a substrate having a conductive pattern according to any one of <1> to <6>, wherein the metal nanobody is a metal nanowire.
<8> The conductive pattern according to any one of <1> to <7>, wherein the metal nanobody is a nanoparticle having an aspect ratio of 1:1 to 1:10 and an equivalent spherical diameter of 1 nm to 200 nm. Substrate manufacturing method.
<9> The method for producing a substrate having a conductive pattern according to any one of <1> to <8>, wherein the metal nanobody is a nanobody of silver or a silver compound.
<10> The conductive pattern according to any one of <1> to <9>, further forming a conductive pattern d′ on the surface of the substrate opposite to the surface on which the conductive layer a is provided. Substrate manufacturing method.
<11> The method for producing a substrate having a conductive pattern according to <1>, wherein the resin layer b contains a compound e capable of bonding or coordinating with the metal contained in the metal nanobody.
<12> The method for producing a substrate having a conductive pattern according to <11>, wherein the compound e is a compound having a lone pair of electrons.
<13> The conductive pattern according to <12>, wherein the compound e is at least one compound selected from the group consisting of a nitrogen-containing compound having a lone pair of electrons and a sulfur-containing compound having a lone pair of electrons. Substrate manufacturing method.
<14> Production of a substrate having a conductive pattern according to any one of <1> to <13>, wherein the photosensitive resin layer c contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. Method.
<15> The substrate having a conductive pattern according to any one of <1> to <13>, wherein the photosensitive resin layer c contains a resin whose polarity changes under the action of acid and a photoacid generator. Production method.
<16> Production of a substrate having a conductive pattern according to any one of <1> to <13>, wherein the photosensitive resin layer c contains a resin having a structural unit having a phenolic hydroxyl group and a quinonediazide compound. Method.
<17> The method for producing a substrate having a conductive pattern according to any one of <1> to <16>, wherein the photosensitive resin layer c is formed of a photosensitive transfer material.
<18> The method for producing a substrate having a conductive pattern according to any one of <1> to <17>, further comprising an intermediate layer on the photosensitive resin layer c.
<19> The process according to <1>, wherein step 5a is a step of softening at least one of the resin 1 and the resin 2 by heat treatment, and filling the voids generated by removing the metal nano-body by the etching. A method for manufacturing a substrate having a conductive pattern.
<20> The method for producing a substrate having a conductive pattern according to <19>, wherein the heat treatment in step 5a is performed at a heating temperature that satisfies Tgp<Th<Tgb.
In addition, Th represents the maximum temperature (° C.) during the heat treatment in step 5a, Tgp represents the lower temperature (° C.) of the glass transition temperature of resin 1 and the glass transition temperature of resin 2, and Tgb represents the substrate. represents the glass transition temperature (°C) of
<21> Manufacture of a substrate having a conductive pattern according to <2>, wherein step 5b is a step of softening the resin 1 by heat treatment and filling voids generated by removing the metal nano-body by the etching. Method.
<22> Step 5a is a step of swelling at least one of the resin 1 and the resin 2 during or after the step 4 and filling the voids generated by the removal of the metal nano-body by the etching. The method for producing a substrate having a conductive pattern according to <1>.
<23> The process described in <2>, wherein step 5b is a step of swelling the resin 1 during or after the step 4 and filling the voids generated by the removal of the metal nano-body by the etching. A method of manufacturing a substrate having a conductive pattern of
<24> A method for producing an electronic device comprising a substrate having a conductive pattern obtained by the method for producing a substrate having a conductive pattern according to any one of <1> to <23>.

<25> A substrate, a first section in which a conductive pattern d containing a metal nano-body and resin 1 is formed on at least one surface of the substrate, and a second section in which the conductive pattern d is not formed. and the area where voids are observed when the second section is observed with a scanning electron microscope from the thickness direction of the substrate is 10% or less of the total area of the second section. A substrate with a conductive pattern.
<26> The substrate having the conductive pattern according to <25>, wherein the resin 1 is present in the second section.
<27> When the layer thickness of the first section from the substrate surface is H1, and the layer thickness of the second section from the substrate surface is H2, 0.90 ≤ H1/H2 ≤ 1 A substrate having the conductive pattern according to <26> satisfying .11.
<28> The substrate having a conductive pattern according to <26> or <27>, wherein the number of recesses having a depth of 10 nm or more in the second section is 10/100 μm ^{2 or} less.

<29> A protective film for a metal nanobody having a resin layer containing a resin having a glass transition temperature of 150° C. or lower.
<30> The resin having a glass transition temperature of 150° C. or lower contains at least one resin selected from the group consisting of an acrylic resin, a polyester resin, a polyvinyl acetal resin, and a phenol resin. Protective film for metal nano-body.
<31> The resin layer contains an oxime ester photopolymerization initiator, a biimidazole photopolymerization initiator, an alkylphenone photopolymerization initiator, an acetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. The protective film for metal nano bodies according to <29> or <30>, further comprising at least one polymerization initiator selected from the group consisting of:
<32> The protective film for a metal nanobody according to any one of <29> to <31>, wherein the resin layer further contains a polymerizable compound having a functionality of two or more.

According to one embodiment of the present invention, it is possible to provide a method for manufacturing a substrate having a conductive pattern that exhibits excellent dimensional stability after energization.
According to another embodiment of the present invention, it is possible to provide a method of manufacturing an electronic device having a substrate having a conductive pattern obtained by the method of manufacturing a substrate having a conductive pattern.
According to still another embodiment of the present invention, it is possible to provide a substrate or protective film for a metal nano-body having a conductive pattern with excellent dimensional stability of the conductive pattern after energization.

It is a schematic diagram showing an example of the configuration of a photosensitive transfer material. 3 is a schematic plan view showing pattern A; FIG. 3 is a schematic plan view showing a pattern B; FIG.

The contents of the present disclosure will be described below. In addition, although it demonstrates referring attached drawings, a code|symbol may be abbreviate|omitted.
Further, in this specification, a numerical range represented by "to" means a range including the numerical values before and after "to" as lower and upper limits.
Further, in the present specification, "(meth)acrylic" represents both or either acrylic and methacrylic, "(meth)acrylate" represents both or either acrylate and methacrylate, and "(meth) ) acryloyl” refers to either or both acryloyl and methacryloyl.
Furthermore, the amount of each component in the composition herein refers to the sum of the corresponding substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. means quantity.
As used herein, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes not only those having no substituents but also those having substituents. For example, the term “alkyl group” includes not only alkyl groups having no substituents (unsubstituted alkyl groups) but also alkyl groups having substituents (substituted alkyl groups).
In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. The light used for exposure generally includes the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and active rays (active energy rays) such as electron beams. mentioned.
In addition, chemical structural formulas in this specification may be described as simplified structural formulas in which hydrogen atoms are omitted.
In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Moreover, in the present disclosure, a combination of two or more preferred aspects is a more preferred aspect.
As used herein, “transparent” means that the average transmittance of visible light with a wavelength of 400 nm to 700 nm is 80% or more, preferably 90% or more.
As used herein, the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
In addition, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation). It is a molecular weight converted using polystyrene as a standard substance detected with a solvent THF (tetrahydrofuran) and a differential refractometer using a gel permeation chromatography (GPC) analyzer.
As used herein, "total solid content" refers to the total mass of components excluding the solvent from the total composition of the composition. Moreover, as described above, the “solid content” is the component excluding the solvent, and may be solid or liquid at 25° C., for example.

(Method for manufacturing a substrate having a conductive pattern)
A first embodiment of the method for manufacturing a substrate having a conductive pattern according to the present disclosure includes step 1a of forming a conductive layer a containing a metal nano-body and resin 1 on a substrate, resin 2 on the conductive layer a. Step 1b of forming a resin layer b containing the Step 3 of obtaining a pattern c', Step 4 of removing the metal nano-body in the conductive layer a by etching to form a conductive pattern d, and Step 4 of softening or swelling at least one of the resin 1 and the resin 2. 5a.
A second embodiment of the method for manufacturing a substrate having a conductive pattern according to the present disclosure includes step 1a of forming a conductive layer a containing a metal nanobody and a resin 1 on a substrate, a photosensitive Step 2b of forming a resin layer c, Step 3 of obtaining a resin pattern c′ of the photosensitive resin layer by exposing and developing the photosensitive resin layer c, and etching to remove the metal nano-body in the conductive layer a. It includes a step 4 of removing and forming a conductive pattern d, and a step 5b of softening or swelling the resin 1 .

In the present specification, when simply referring to "a method for manufacturing a substrate having a conductive pattern according to the present disclosure" without any particular mention, it refers to all of the first embodiment and the second embodiment. . In addition, when simply referring to "step 1a" and the like without any particular notice, all steps 1a and the like of the first embodiment and the second embodiment will be described.

Conventionally, transparent wiring made of metal oxides (indium tin oxide (ITO), indium zinc oxide (IZO), etc.), which has been used in the viewing portion of touch panel substrates, is inferior in flexibility. There is a problem in using it as a wiring board. Also, from the viewpoint of low power consumption, replacement of these metal oxide wirings is desired.
As one means for solving such a problem of flexibility, a technique for forming wiring by using a structure in which a metal nanobody, especially a metal nanowire is dispersed in a resin, as a conductive layer has been developed in recent years. In such a structure, the metal nanoparticles dispersed in the resin exhibit conductivity by having many contacts with each other. The change in resistance is extremely small because it is unlikely that all of the multiple contacts between the nano bodies are broken at the same time. In particular, by using a metal nanowire as the metal nanobody, it is possible to obtain a very low resistance value and deformation resistance, and it has properties suitable as a wiring material.
However, conventionally, when a conductive pattern is formed from a conductive layer containing a metal nanobody and a resin, the metal nanobody is dispersed in resin or the like, so only the metal nanobody dissolves during etching, and the resin portion remains as it is. It is often seen that This is because the resin used for dispersing the metal nanoparticles is often hydrophobic from the viewpoint of dispersion stability, oxidation prevention of the metal nanoparticles, etc., and is not compatible with the aqueous solution used for etching.
In this case, the etched portion remains as voids where the metal nano-body is dissolved, and becomes an insulating portion substantially free of the nano-body.

Voids in the present disclosure are traces of removal of metal nano-objects. For this reason, the depth of the dents in the voids is often greater than the depth of the dents present in the conductive layer a or the resin layer b where the metal nano-body does not exist.
Specifically, the maximum valley depth Rv1 of the portion of the conductive layer a or the resin layer b where no metal nano-body exists and the maximum valley depth Rv2 of the resin portion left after the etching of the conductive layer a are Measured using a microscope (AFM), it is often Rv2>Rv1. As the void, there may be a state in which a part of the thickness of the resin portion left after the etching of the conductive layer a is recessed, a state in which the base material is penetrated, and the like. For example, when the average thickness of the conductive layer a is 10 nm and Rv1 is 1 nm, the depth of the void is often greater than 1 nm and less than or equal to 10 nm.
In addition, since the voids in the present disclosure are traces of removal of metal nano-bodies dispersedly present in the conductive layer, dents generated by patterning the conductive layer itself (for example, through holes formed in the conductive layer case) is not a void.
Moreover, the voids can take various forms depending on the shape of the metal nano-body. The voids due to spherical nanoparticles are circular, and the voids due to rod-like or filamentous nanowires are channel-like.

When a substrate having a conductive pattern with such voids remaining is energized, the metal nanoparticles in the conductive pattern are oxidized due to water contamination in the voids, etching residue, etc., and the ionized metal flows through the voids. Diffusion phenomena may occur. The diffused metal is reduced in another part of the circuit and deposited as metal. The present inventors have found that this metal migration phenomenon causes problems such as a decrease in circuit width and deposition of metal, and causes a problem in the dimensional stability of the conductive pattern after energization.
A method for manufacturing a substrate having a conductive pattern according to the present disclosure uses a conductive layer containing a metal nanobody and a resin, forms a resin pattern on the conductive layer, and removes the conductive layer in a portion where the resin pattern is not formed. Even when removed by etching, the dimensional stability of the conductive pattern after energization is excellent.

Hereinafter, a method for manufacturing a substrate having a conductive pattern according to the present disclosure will be described in detail.

<Gap>
In the method for manufacturing a substrate having a conductive pattern according to the present disclosure, at least one surface of the obtained substrate having a conductive pattern has a first section on which the conductive pattern d is formed and the conductive pattern d is formed. It is preferable to have a second section that is not filled, and from the viewpoint of dimensional stability of the conductive pattern after energization, the second section is observed with a scanning electron microscope from the thickness direction of the substrate. More preferably, the observed area is 10% or less of the total area of the second compartment, and the area of the observed void is 8% or less of the total area of the second compartment. More preferably, the area where the voids are observed is particularly preferably 5% or less of the total area of the second compartment, and the area where the voids are observed is the second Most preferably, it is 0% or more and 3% or less with respect to the total area of the compartment.

A method for measuring the area where voids are observed in the second section of the substrate having the conductive pattern is as follows.
A portion of the substrate having the conductive pattern where the conductive pattern does not exist (second section) is observed with a scanning electron microscope from a direction perpendicular to the surface direction of the substrate for voids present in 100 μm square. The gap portion of the observed image is binarized, and the ratio of the number of pixels occupying the observation field of view is defined as the ratio of the number of pixels (the ratio of the area where the gap is observed). Observations are made at three different locations on the sample, and the average value is taken as the porosity of the sample.

<Step 1a>
A method for manufacturing a substrate having a conductive pattern according to the present disclosure includes step 1a of forming a conductive layer a containing metal nano-body and resin 1 on a substrate.
The material of the metal nanobody contained in the conductive layer a includes copper, silver, zinc, iron, chromium, molybdenum, nickel, aluminum, gold, platinum, palladium, an alloy of two or more of these, and ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), conductive silica, etc. can be used, but from the viewpoint of resistance value, cost, sintering temperature, etc., copper, silver, nickel, aluminum, gold, platinum, palladium, or these is preferred, silver, copper or alloys thereof are more preferred, silver or a silver alloy is more preferred particularly from the viewpoint of sintering temperature and oxidation suppression, and silver is particularly preferred. That is, the metal nanobody is particularly preferably a silver or silver compound nanobody.
The shape of the metal nanobody is not particularly limited as long as it has a known shape, but the metal nanobody is preferably a metal nanoparticle or a metal nanowire, more preferably a metal nanowire.

Examples of the shape of the metal nanowires include a cylindrical shape, a rectangular parallelepiped shape, and a columnar shape having a polygonal cross section. Metal nanowires preferably have at least one of a columnar shape and a columnar shape with a polygonal cross section in applications where high transparency is required.
The cross-sectional shape of metal nanowires can be observed, for example, using a transmission electron microscope (TEM).

The diameter of the metal nanowires (so-called minor axis length) is not particularly limited, but for example, from the viewpoint of transparency, it is preferably 50 nm or less, more preferably 35 nm or less, and further preferably 20 nm or less. preferable.
The lower limit of the diameter of the metal nanowires is preferably 5 nm or more, for example, from the viewpoint of oxidation resistance and durability.

The length of the metal nanowires (so-called long axis length) is not particularly limited, but from the viewpoint of conductivity, it is preferably 5 μm or more, more preferably 10 μm or more, and 30 μm or more. More preferred.
The upper limit of the length of the metal nanowires is preferably 1 mm or less, for example, from the viewpoint of suppressing the formation of aggregates in the manufacturing process.

The diameter and length of metal nanowires can be measured using, for example, a transmission electron microscope (TEM) or an optical microscope.
Specifically, the diameter and length of 300 randomly selected metal nanowires are measured from the metal nanowires observed under magnification using a transmission electron microscope (TEM) or an optical microscope. The measured values are arithmetically averaged, and the obtained values are taken as the diameter and length of the metal nanowires.

The metal nanoparticles may be spherical particles, tabular particles, or irregularly shaped particles.
The average primary particle size of the metal nanoparticles is preferably 0.1 nm to 500 nm, more preferably 1 nm to 200 nm, particularly preferably 1 nm to 100 nm, from the viewpoint of stability and fusion temperature.
The average primary particle size of the metal nanoparticles in the present disclosure is obtained by taking a scanning electron micrograph (SEM image) of 100 particles with a scanning electron microscope (eg, S-3700N, manufactured by Hitachi High-Technologies Corporation). It can be obtained by measuring the particle size using an image processing measuring device (Luzex AP; manufactured by Nireco Corporation) and calculating the arithmetic mean value. That is, the particle size referred to in the present disclosure is represented by the diameter when the projected shape of the particle is circular, and is represented by the diameter of a circle having the same area as the projected area when the particle is irregular other than spherical. .

From the viewpoint of conductivity, the metal nanoparticles preferably contain a metal nobler than silver, and in this case, more preferably flat particles at least partially coated with gold. Here, "a metal more noble than silver" means "a metal having a standard electrode potential higher than that of silver".
The ratio of the metal nobler than silver to silver in the metal nanoparticles is preferably 0.01 atomic % to 5 atomic %, more preferably 0.1 atomic % to 2 atomic %, and 0.1 atomic % to 5 atomic %. It is more preferably 2 atomic % to 0.5 atomic %.
The content of metals nobler than silver can be measured, for example, by inductively coupled plasma (ICP) emission spectrometry after dissolving a sample with an acid or the like.

From the viewpoint of dispersibility and conductivity, the metal nanobody is preferably a nanoparticle having an aspect ratio of 1:1 to 1:10 and an equivalent spherical diameter of 1 nm to 200 nm.

The metal nano-body in the conductive layer a may be used alone or in combination of two or more.
The content of the metal nanobody is preferably 1% by mass to 99% by mass, more preferably 1% by mass to 95% by mass, based on the total mass of the conductive layer a, from the viewpoint of conductivity and dispersion stability. is more preferable, and more preferably 1% by mass to 90% by mass.

From the viewpoint of durability, the resin 1 contained in the conductive layer a is preferably a binder polymer.
Examples of the resin 1 include acrylic resin [e.g., poly(methyl methacrylate)], polyester resin [e.g., polyethylene terephthalate (PET)], polycarbonate resin, polyimide resin, polyamide resin, polyolefin (e.g., polypropylene), polynorbornene. , cellulose resin, polyvinyl alcohol (PVA), polyvinylpyrrolidone, and the like.
Cellulose resins include hydroxypropylmethylcellulose (HPMC), hydroxyethylcellulose (HEC), methylcellulose (MC), hydroxypropylcellulose (HPC), carboxymethylcellulose (CMC), cellulose and the like.
Also, the resin 1 may be a conductive polymer material.
Examples of conductive polymer materials include polyaniline and polythiophene.
Among them, Resin 1 is at least one resin selected from the group consisting of cellulose resin, polyvinyl alcohol, and polyvinylpyrrolidone, from the viewpoint of the dispersibility of the metal nano-body and the dimensional stability of the conductive pattern after energization. and more preferably a cellulose resin.

The glass transition temperature (Tg) of Resin 1 is preferably 180° C. or less, more preferably 40° C. to 160° C., more preferably 60° C. to 150° C., from the viewpoint of dimensional stability of the conductive pattern after energization. is particularly preferred.

In this disclosure, the glass transition temperature of a resin can be measured using differential scanning calorimetry (DSC).
A specific measuring method is performed according to the method described in JIS K 7121 (1987) or JIS K 6240 (2011). As the glass transition temperature in this specification, an extrapolated glass transition start temperature (hereinafter sometimes referred to as Tig) is used.
A method for measuring the glass transition temperature will be described more specifically.
When determining the glass transition temperature, after holding the apparatus at a temperature about 50° C. below the expected Tg of the resin until it stabilizes, heating rate: 20° C./min. Heat to elevated temperature and generate a differential thermal analysis (DTA) curve or DSC curve.
The extrapolated glass transition start temperature (Tig), that is, the glass transition temperature Tg in this specification, is a straight line obtained by extending the baseline on the low temperature side of the DTA curve or DSC curve to the high temperature side, and the stepwise change part of the glass transition. It is obtained as the temperature at the point of intersection with the tangent line drawn at the point where the slope of the curve is maximum.

The resin 1 in the conductive layer a may be used alone or in combination of two or more.
The content of Resin 1 is preferably 1% by mass to 90% by mass, preferably 10% by mass, with respect to the total mass of the conductive layer a, from the viewpoint of metal film formation during sintering and electrical conductivity. It is more preferably 80 mass %, particularly preferably 20 mass % to 70 mass %.

The conductive layer a may further contain other additives.
Other additives include known additives such as surfactants.
Surfactants include Rapisol A-90 (manufactured by NOF Corporation, solid content concentration 1%), Naloacty CL-95 (manufactured by Sanyo Chemical Industries, Ltd., solid content concentration 1%), and the like. .
Moreover, the conductive layer a may contain inorganic particles.
Inorganic particles include silica, mullite, alumina and the like.

The conductive layer a preferably has high transparency, and preferably has a transmittance of 60% or more, more preferably 70% or more, to light with a wavelength of 380 nm to 780 nm.

The thickness of the conductive layer a is not limited. The average thickness of the conductive layer a is preferably 0.001 μm to 1,000 μm, more preferably 0.005 μm to 15 μm, more preferably 0.01 μm to 10 μm is particularly preferred.
The average thickness of each layer and substrate in the present disclosure is the average value of 10 thicknesses measured by observing a cross section perpendicular to the in-plane direction using a scanning electron microscope (SEM). and

The method of forming the conductive layer a is not particularly limited, but it is preferably formed by applying a material in which the conductive material containing the metal nano-body is dispersed in a liquid, that is, by applying a conductive ink.
In addition, the method of applying the conductive ink is not particularly limited, but includes an inkjet method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a die coating method (that is, a slit coating method), and the like. .
The conductive inks used in the present disclosure may be curable, such as heat-curable, light-curable, or heat and light-curable.
The conductive ink contains a metal nanomaterial and a resin, and may further contain at least one of the solvent and the other additives.
Water and an organic solvent can be used as the solvent contained in the conductive ink.
Preferred organic solvents include hydrocarbons such as toluene, dodecane, tetradecane, cyclododecene, n-heptane and n-undecane, and alcohols such as ethanol and isopropyl alcohol.
The method for forming the conductive layer a may include steps such as drying and baking after coating, if necessary.

Moreover, the conductive layer a is preferably formed in a shape larger than the shape of the desired conductive pattern.

A known substrate may be used as the substrate used in the method for manufacturing a substrate having a conductive pattern according to the present disclosure, and may have any layer other than the conductive layer as necessary.
Examples of substrates include resin substrates, glass substrates, and semiconductor substrates.
Preferred embodiments of the substrate include, for example, those described in paragraph 0140 of WO2018/155193, the contents of which are incorporated herein.

Base materials that constitute the substrate include, for example, glass, silicon, and films.
The base material constituting the substrate is preferably transparent.
Transparent glass substrates include tempered glass such as Corning Gorilla Glass. Materials used in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492 can be used as the transparent glass substrate.

When a film substrate is used as the substrate, it is preferable to use a film substrate with low optical distortion and/or high transparency. Such film substrates include, for example, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, polyimides and cycloolefin polymers.

As the substrate, a film substrate is preferable when manufacturing by a roll-to-roll method. Moreover, when manufacturing the circuit wiring for touchscreens by a roll-to-roll method, it is preferable that a board|substrate is a sheet-shaped resin composition.

The substrate may have the conductive layer a alone, or may have two or more layers. When it has two or more conductive layers a, it is preferable to have conductive layers made of different materials.
Further, the substrate may have the conductive layer a on only one surface or on both surfaces.

Further, the substrate may be a substrate further having lead-out wiring. The substrate as described above can be suitably used as a touch panel substrate.
A metal is preferable as the material of the routing wiring.
Examples of metals for the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, manganese, and alloys composed of two or more of these metal elements. Copper, molybdenum, aluminum, or titanium is preferable as the material of the routing wiring, and copper is particularly preferable.

<Step 1b>
A first embodiment of the method for manufacturing a substrate having a conductive pattern according to the present disclosure includes step 1b of forming a resin layer b (also referred to as a "protective layer") containing a resin 2 on the conductive layer a. .

Examples of resin 2 include acrylic resins (e.g., Mitsubishi Chemical Co., Ltd. DIANAL series, Nippon Shokubai Acryset series, etc.), polyester resins (e.g., Unitika Co., Ltd. ELITEL series, Mitsubishi Chemical Co., Ltd. ) Nichigo polyester series, etc.), polyvinyl alcohol resin (e.g., Kuraray Poval series, etc.), polyvinyl acetal resin (e.g., Sekisui Chemical Co., Ltd. S-lec series, etc.), phenolic resin (e.g., DIC Phenolite series manufactured by Co., Ltd., etc.) are preferably mentioned.
Among them, the resin 2 preferably contains at least one resin selected from the group consisting of an acrylic resin, a polyester resin, a polyvinyl acetal resin, and a phenol resin, from the viewpoint of the dimensional stability of the conductive pattern after energization. , a polymer having a structural unit derived from benzyl (meth)acrylate, and at least one resin selected from the group consisting of polyester resins.

The glass transition temperature (Tg) of the resin 2 is preferably 150° C. or less, more preferably 30° C. to 140° C., more preferably 40° C. to 130° C., from the viewpoint of the dimensional stability of the conductive pattern after energization. and particularly preferably 40°C to 120°C.

The acid value of the resin 2 is preferably 0 mgKOH/g to 60 mgKOH/g, more preferably 0 mgKOH/g to 50 mgKOH/g, from the viewpoint of etching resistance and dimensional stability of the conductive pattern after energization. More preferably, 0 mgKOH/g to 40 mgKOH/g is particularly preferred.
The acid value of Resin 2 can be measured by the method described below.

The resin 2 in the resin layer b may be used alone or in combination of two or more.
The content of the resin 2 is preferably 40% by mass to 100% by mass, preferably 50% by mass, based on the total mass of the resin layer b from the viewpoint of metal film formation during sintering and conductivity. It is more preferably 95 mass %, particularly preferably 55 mass % to 90 mass %.

The resin layer b may contain a polymerizable compound.
When the resin layer b contains a polymerizable compound, the resin layer b preferably contains a polymerizable compound and a polymerization initiator.
From the viewpoint of curability, the polymerizable compound is preferably an ethylenically unsaturated compound, more preferably a (meth)acrylate compound.
Further, as the polymerizable compound, from the viewpoint of curability and strength of the resin layer b, it preferably contains a bifunctional or higher polymerizable compound, and more preferably contains a trifunctional to decafunctional polymerizable compound. , tetrafunctional to octafunctional polymerizable compounds are particularly preferred.
Further, the polymerizable compound preferably contains a bifunctional or higher ethylenically unsaturated compound, more preferably a bifunctional or higher (meth)acrylate compound, from the viewpoint of curability and strength of the resin layer b. .
Moreover, as a polymerizable compound, a polymerizable compound used for a photosensitive resin layer, which will be described later, can also be suitably used.

The polymerizable compound in the resin layer b may be used alone or in combination of two or more.
From the viewpoint of the strength of the resin layer b, the content of the polymerizable compound is preferably 5% by mass to 55% by mass, more preferably 10% by mass to 50% by mass, with respect to the total mass of the resin layer b. is more preferred, and 20% by mass to 45% by mass is particularly preferred.

The polymerization initiator is preferably a photopolymerization initiator.
The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used.
As the photopolymerization initiator, a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as an “oxime photopolymerization initiator”), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter, “α- Also referred to as "aminoalkylphenone-based photopolymerization initiator".), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as an "α-hydroxyalkylphenone-based polymerization initiator"), an acylphosphine oxide structure A photopolymerization initiator having Also referred to as "agent".) and the like.
Among them, from the viewpoint of curability, the resin layer b contains an oxime ester photopolymerization initiator, a biimidazole photopolymerization initiator, an alkylphenone photopolymerization initiator, an acetophenone photopolymerization initiator, and an acylphosphine. It preferably contains at least one polymerization initiator selected from the group consisting of oxide-based photopolymerization initiators, and more preferably contains an oxime ester-based photopolymerization initiator.

The polymerization initiator in the resin layer b may be used alone or in combination of two or more.
From the viewpoint of the strength of the resin layer b, the content of the polymerization initiator is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, based on the total mass of the resin layer b. %, and particularly preferably 0.5% by mass to 5% by mass.

From the viewpoint of adhesion with the conductive layer a and dimensional stability of the conductive pattern after energization, the resin layer b may contain a compound e capable of bonding or coordinating with the metal contained in the metal nano-body. preferable.
The compound e is preferably a compound having a lone pair of electrons from the viewpoint of coordinating property and dimensional stability of the conductive pattern after energization. It is more preferably at least one compound selected from the group consisting of sulfur-containing compounds having a pair, and particularly preferably a nitrogen-containing compound having a lone pair.
In addition, the compound e is preferably a heterocyclic compound from the viewpoint of coordinating property and dimensional stability of the conductive pattern after energization, such as a nitrogen-containing heterocyclic compound, a sulfur-containing heterocyclic compound, Alternatively, a nitrogen-containing and sulfur-containing heterocyclic compound is more preferable, and a nitrogen-containing heterocyclic compound is particularly preferable.
Furthermore, the nitrogen-containing heterocyclic compound preferably has a heterocyclic ring having two or more nitrogen atoms, from the viewpoint of coordinating property and dimensional stability of the conductive pattern after energization, and three or more nitrogen atoms. It is more preferred to have heterocycles with 3 or 4 nitrogen atoms, especially heterocycles with 3 or 4 nitrogen atoms.

The heterocyclic ring contained in the heterocyclic compound may be either monocyclic or polycyclic heterocyclic ring.
A nitrogen atom, an oxygen atom, and a sulfur atom are mentioned as a heteroatom which a heterocyclic compound has. The heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a nitrogen atom.

Preferred examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds. be done. Among the above, from the viewpoint of adhesion to the conductive layer a, the heterocyclic compound is a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzimidazole compound, and a benzo It is preferably at least one compound selected from the group consisting of oxazole compounds, triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds. It is more preferably at least one compound selected from the group consisting of, more preferably at least one compound selected from the group consisting of a triazole compound and a tetrazole compound, and particularly preferably a triazole compound.

Preferred specific examples of the heterocyclic compound are shown below. Examples of triazole compounds and benzotriazole compounds include the following compounds.

Examples of tetrazole compounds include the following compounds.

Examples of thiadiazole compounds include the following compounds.

Examples of triazine compounds include the following compounds.

Examples of rhodanine compounds include the following compounds.

Examples of thiazole compounds include the following compounds.

Examples of benzothiazole compounds include the following compounds.

Examples of benzimidazole compounds include the following compounds.

Examples of benzoxazole compounds include the following compounds.

Preferred sulfur-containing compounds include thiol compounds and disulfide compounds.
Preferred thiol compounds include aliphatic thiol compounds.
As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a bifunctional or higher aliphatic thiol compound) is preferably used.
Examples of polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate ), tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate pionate), dipentaerythritol hexakis(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1, 3-propanedithiol, 1,6-hexamethylenedithiol, 2,2′-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl)ether.
Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n- Octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

Disulfide compounds include 2-(4′-morpholinodithio)benzthiazole, 2,2′-benzthiazolyl disulfide, bis(2-benzamidophenyl) disulfide, 1,1-thiobis(2-naphthol), bis( 2,4,5-trichlorophenyl) disulfide, 4,4'-dithiomorpholine, tetraethylthiuram disulfide, dibenzyl disulfide, bis(2,4-dinitrophenyl) disulfide, 4,4'-diaminodiphenyl disulfide, diallyl disulfide , di-tert-butyl disulfide, bis(6-hydroxy-2-naphthyl) disulfide, dicyclohexyl disulfide, o-isobutyroylthiamine disulfide, diphenyl disulfide.

Further, the molecular weight of the compound e is preferably less than 1,000, more preferably 50 to 500, even more preferably 50 to 200, from the viewpoint of adhesion with the conductive layer a. 50-150 is particularly preferred.

The compound e in the resin layer b may be used alone or in combination of two or more.
From the viewpoint of adhesion with the conductive layer a, the content of the compound e is preferably 0.01% by mass to 20% by mass, and preferably 0.1% by mass to 20% by mass, based on the total mass of the resin layer b. It is more preferably 10 mass %, still more preferably 0.3 mass % to 8 mass %, and particularly preferably 0.5 mass % to 5 mass %.

In addition, the resin layer b may contain other known additives.

The average thickness of the resin layer b is not particularly limited, but is preferably 1 nm to 200 nm, more preferably 5 nm to 100 nm, more preferably 15 nm to 50 nm, from the viewpoint of dimensional stability of the conductive pattern after energization. is particularly preferred.

The total thickness of the layer a and the layer b after forming the resin layer b on the conductive layer a is preferably 15 nm to 100 nm, more preferably 15 nm to 90 nm, and particularly preferably 15 nm to 60 nm. In this case, the total thickness of the layer a and the layer b may or may not be equal to the sum of the layer thicknesses when each layer is formed independently. For example, when the compatibility between the resins contained in the layers a and b is high, a layer is formed in which the materials of the layers a and b are partially mixed. The total thickness of the layers is no longer equal to the sum of the layer thicknesses of each layer formed separately.

<Step 2a and Step 2b>
A first embodiment of the method for manufacturing a substrate having a conductive pattern according to the present disclosure includes step 2a of forming a photosensitive resin layer c on the resin layer b.
A second embodiment of the method for manufacturing a substrate having a conductive pattern according to the present disclosure includes step 2b of forming a photosensitive resin layer c on the conductive layer a.
A method for forming the photosensitive resin layer c on the conductive layer a or the resin layer b is not particularly limited, and a known resist forming method can be used. Among them, the steps 2a and 2b are preferably steps of forming the photosensitive resin layer c by contacting and transferring a photosensitive transfer material onto the conductive layer a or the resin layer b.
Steps 2a and 2b are preferably steps of forming a photosensitive resin layer c and an intermediate layer in this order on the conductive layer a or the resin layer b, and the intermediate layer is a water-soluble resin layer. , and more preferably a thermoplastic resin layer.
As a method of transferring the photosensitive resin layer c onto the conductive layer a or the resin layer b using a photosensitive transfer material, the conductive layer a or the resin layer b is transferred onto the photosensitive resin layer c of the photosensitive transfer material. are brought into contact with each other, and the photosensitive transfer material and the conductive layer a or the resin layer b are pressure-bonded. In the above aspect, the adhesion between the photosensitive resin layer c and the conductive layer a or the resin layer b in the photosensitive transfer material is improved, so that the patterned photosensitive resin layer c after exposure and development is , can be suitably used as an etching resist when etching the conductive layer.
Preferred aspects of the photosensitive transfer material used in the method for manufacturing a substrate having a conductive pattern according to the present disclosure will be collectively described later.

The photosensitive resin layer c may be a positive photosensitive resin layer or a negative photosensitive resin layer.
Any of the following aspects of the photosensitive resin layer c can be preferably mentioned.
A mode in which the photosensitive resin layer c contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator The photosensitive resin layer c is a resin (preferably acid-decomposable) whose polarity changes under the action of acid A mode containing a resin (that is, a polymer having a structural unit having an acid group protected by an acid-decomposable group) and a photoacid generator The photosensitive resin layer c has a structural unit having a phenolic hydroxyl group An embodiment containing a resin and a quinonediazide compound

The method for press-bonding the conductive layer a or the resin layer b to the photosensitive transfer material is not particularly limited, and known transfer methods and lamination methods can be used.
The photosensitive transfer material is laminated to the conductive layer a or the resin layer b by bonding the outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer c with respect to the temporary support and the conductive layer a or the resin layer. It is preferably carried out by stacking the layer b and applying pressure and heat using means such as rolls. A known laminator such as a laminator, a vacuum laminator, and an autocut laminator that can further improve productivity can be used for the lamination.
Although the lamination temperature is not particularly limited, it is preferably 70° C. to 130° C., for example.

The method of manufacturing a substrate having a conductive pattern according to the present disclosure is preferably performed by a roll-to-roll method.
The roll-to-roll method will be described below.
The roll-to-roll method uses a substrate that can be wound and unwound as a substrate, and before any step included in the method for manufacturing a substrate having a conductive pattern according to the present disclosure, the substrate or the conductive A step of unwinding a substrate having layers and the like (also referred to as an “unwinding step”), and a step of winding the substrate having the conductive layers and the like after any of the steps (also referred to as a “winding step”). , and at least one of the steps (preferably all steps or all steps other than the heating step) is performed while the substrate or the substrate having the conductive layer or the like is being transported.
The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and known methods may be used in manufacturing methods to which a roll-to-roll system is applied.

Further, when the photosensitive transfer material has a protective film, the method for manufacturing a substrate having a conductive pattern according to the present disclosure preferably includes a protective film peeling step of peeling off the protective film before Step 2a or Step 2b. .
A method for peeling off the protective film is not limited, and a known method can be applied.

In the case of using the above-mentioned photosensitive transfer material, the method for manufacturing a substrate having a conductive pattern according to the present disclosure includes the In addition, it is preferable to include a temporary support peeling step of peeling off the temporary support.
The peeling method of the temporary support is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs 0161 to 0162 of JP-A-2010-072589 can be used.

<Step 3>
A method for manufacturing a substrate having a conductive pattern according to the present disclosure includes step 3 of obtaining a resin pattern c′ of the photosensitive resin layer on the substrate by exposing and developing the photosensitive resin layer c.
The exposure in step 3 is patterned exposure processing (also referred to as “pattern exposure”), that is, exposure processing in which exposed portions and non-exposed portions exist.
The positional relationship between the exposed area and the unexposed area in pattern exposure is not particularly limited, and is adjusted as appropriate.

The detailed arrangement and specific size of the pattern in pattern exposure are not particularly limited. For example, at least part of the pattern (preferably The electrode pattern and/or lead-out wiring portion of the touch panel) preferably includes fine lines with a width of 20 μm or less, and more preferably includes fine lines with a width of 10 μm or less.
In addition, from the viewpoint of further exerting the effects of the present disclosure, the obtained resin pattern preferably has a resin pattern with a line width of 20 μm or less, and more preferably has a resin pattern with a line width of 10 μm or less. It is more preferable to have a resin pattern with a line width of 8 μm or less, and it is particularly preferable to have a resin pattern with a line width of 5 μm or less.

The light source used for exposure can be appropriately selected and used as long as it is a light source that irradiates light of a wavelength (for example, 365 nm, 405 nm, or 436 nm) with which the photosensitive resin layer c can be exposed. Specifically, ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps and LEDs (Light Emitting Diodes) are included.
The exposure dose is preferably 5 mJ/cm ² to 200 mJ/cm ² , more preferably 10 mJ/cm ² to 100 mJ/cm ² .
Preferred embodiments of the light source, exposure amount and exposure method used for exposure include, for example, paragraphs 0146 to 0147 of WO 2018/155193, the contents of which are incorporated herein.

When a photosensitive transfer material is used, in step 3, pattern exposure may be performed after peeling the temporary support from the transfer layer (photosensitive resin layer c and intermediate layer), and before peeling the temporary support, Pattern exposure may be performed through a temporary support, and then the temporary support may be peeled off. When the temporary support is peeled off before exposure, the mask may be brought into contact with the transfer layer for exposure, or may be brought close to the transfer layer for exposure without contact. When exposure is performed without peeling off the temporary support, the mask may be exposed in contact with the temporary support, or may be exposed in close proximity without contact. In order to prevent contamination of the mask due to contact between the transfer layer and the mask and to avoid the influence of foreign matter adhering to the mask on the exposure, it is preferable to carry out pattern exposure without peeling off the temporary support. The exposure method is a contact exposure method in the case of contact exposure, a proximity exposure method in the case of a non-contact exposure method, a projection exposure method using a lens system or a mirror system, a direct exposure method using an exposure laser or the like. An exposure (direct drawing exposure) method can be appropriately selected and used. In the case of projection exposure using a lens system or a mirror system, an exposure machine having an appropriate lens numerical aperture (NA) can be used according to the required resolving power and depth of focus. In the case of the direct exposure method, drawing may be performed directly on the photosensitive resin layer c, or reduction projection exposure may be performed on the photosensitive resin layer c via a lens. Further, the exposure may be performed not only in the air, but also under reduced pressure or in a vacuum, and the exposure may be performed by interposing a liquid such as water between the light source and the transfer layer.
From the viewpoint of resolution, the exposure in step 3 is preferably carried out by contact exposure by bringing the transfer layer and the mask into contact with each other.
Further, the exposure in step 3 is preferably performed by direct drawing exposure or projection exposure from the viewpoint of reducing the influence on the mask and the photosensitive resin layer.

The development treatment in step 3 is preferably carried out with a developer.
The developer is not particularly limited as long as it can remove the non-image portion (unnecessary portion) of the photosensitive resin layer c. Available.
The developer is preferably an alkaline aqueous solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol/L to 5 mol/L (liter). The developer may contain a water-soluble organic solvent and/or a surfactant.
Alkaline compounds that can be contained in the alkaline aqueous solution include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).
As the developer, the developer described in paragraph 0194 of International Publication No. 2015/093271 is also preferably used. A development method that is preferably used includes, for example, the development method described in paragraph 0195 of International Publication No. 2015/093271.

The development method is not particularly limited, and may be any of puddle development, shower development, shower and spin development, and dip development. Shower development is a development process in which non-image areas are removed by spraying a developing solution onto the photosensitive resin layer after exposure.
After the development step, it is preferable to remove development residues by spraying a cleaning agent with a shower.
Although the liquid temperature of the developer is not particularly limited, it is preferably 20°C to 40°C.

<Step 4>
A method for manufacturing a substrate having a conductive pattern according to the present disclosure includes step 4 of removing metal nano-bodies in the conductive layer a by etching to form a conductive pattern d.
In step 4, the conductive layer a is etched using the resin pattern c' formed from the photosensitive resin layer c as an etching resist.
As the etching method, a known method can be applied, for example, the method described in paragraphs 0209 to 0210 of JP-A-2017-120435, and the method described in paragraphs 0048 to 0054 of JP-A-2010-152155. method, a wet etching method of immersion in an etchant, and a dry etching method such as plasma etching.
Moreover, the removal of the conductive layer a in step 4 is preferably performed by wet etching from the viewpoint of exhibiting the effects of the present disclosure more.

As the etchant used for wet etching, an acidic or alkaline etchant may be appropriately selected according to the object to be etched.
Examples of acidic etching solutions include aqueous solutions of acidic components alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid, and acidic components, iron chloride (II), iron chloride ( III), iron(II) nitrate, iron(III) nitrate, iron(II) sulfate, iron(III) sulfate, ammonium fluoride and potassium permanganate. The acidic component may be a combination of multiple acidic components.
Alkaline etching solutions include aqueous solutions of alkali components alone selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (tetramethylammonium hydroxide, etc.), and alkali components and salts. (potassium permanganate, etc.). The alkaline component may be a component obtained by combining a plurality of alkaline components.
Among them, the etching solution preferably contains at least one selected from the group consisting of iron nitrate and iron sulfate.
In order to control the etching speed and the shape of the material to be etched, it is also preferable to combine other acids, organic solvents, surfactants, amines, inorganic salt agents, and the like.

<Step 5a and Step 5b>
A first embodiment of the method for manufacturing a substrate having a conductive pattern according to the present disclosure includes a step 5a of softening or swelling at least one of the resin 1 and the resin 2.
A second embodiment of the method for manufacturing a substrate having a conductive pattern according to the present disclosure includes a step 5b of softening or swelling the resin 1.
The method for manufacturing a substrate having a conductive pattern according to the present disclosure includes Step 5a or Step 5b, so that at least one of the resin 1 and the resin 2 is removed from the voids generated by removing the metal nano-body in Step 4. It is presumed that the above-mentioned metal migration phenomenon or the like can be suppressed by softening or swelling to eliminate or reduce the size of the conductive pattern, resulting in excellent dimensional stability of the conductive pattern after energization.

Step 5a is preferably a step of softening at least one of resin 1 and resin 2 from the viewpoint of dimensional stability of the conductive pattern after energization, and at least one of resin 1 and resin 2 is softened by heat treatment. and softening at least one of the resin 1 and the resin 2 by heat treatment, and filling the voids generated by the removal of the metal nano-body by the etching. Especially preferred.
From the viewpoint of dimensional stability of the conductive pattern after energization, it is preferable to at least soften or swell the resin 2 in step 5a.

From the viewpoint of the dimensional stability of the conductive pattern after energization, the step 5b is preferably a step of softening the resin 1, more preferably a step of softening the resin 1 by heat treatment. It is particularly preferable that the step of softening the resin 1 and filling the voids generated by the removal of the metal nano-body by the etching.

When step 5a or step 5b is a step of softening the resin, step 5a or step 5b may be performed after step 4 or simultaneously with step 4, that is, during step 4, but step 4 preferably after

When heat treatment is performed in step 5a or step 5b, the heating temperature may be a temperature at which at least one of the resin 1 and the resin 2 is softened. 180°C is more preferred, and 100°C to 160°C is particularly preferred.
The heating time is not particularly limited, but is preferably 1 minute to 24 hours, more preferably 5 minutes to 6 hours, and particularly preferably 10 minutes to 60 minutes.
Moreover, the heating temperature is preferably higher than the lower one of the glass transition temperature of the resin 1 and the glass transition temperature of the resin 2 from the viewpoint of the dimensional stability of the conductive pattern after energization.
Further, the heat treatment in step 5a is particularly preferably performed at a heating temperature that satisfies Tgp<Th<Tgb from the viewpoint of dimensional stability of the conductive pattern after energization.
Note that Th represents the maximum temperature (° C.) during the heat treatment in step 5a, Tgp represents the lower temperature (° C.) of the glass transition temperature of resin 1 and the glass transition temperature of resin 2, and Tgb represents the substrate. represents the glass transition temperature (°C) of

The heating means used in the heat treatment in step 5a or step 5b is not particularly limited, and known heating means can be used. and a high-frequency heater and the like.

Further, step 5a is preferably a step of swelling at least one of the resin 1 and the resin 2 during or after step 4, and during or after step 4, the resin 1 and the resin 2 is swollen, and the voids generated by the removal of the metal nano-body by the etching are preferably filled.
The step 5b is preferably a step of swelling the resin 1 during the step 4 or after the step 4. During or after the step 4, the resin 1 is swollen and the etching is performed. It is more preferable to fill the voids generated by removing the metal nano-body.
The swelling can be preferably carried out by bringing the resin 1 or the resin 2 into contact with a known solvent such as water or an organic solvent.
Above all, the swelling is preferably carried out with an etchant in step 4.
The temperature during swelling and the contact time with the solvent are not particularly limited and can be selected as appropriate.

<Resin pattern removal process>
The method for manufacturing a substrate having a conductive pattern according to the present disclosure preferably includes a step of removing the remaining resin pattern c' (resin pattern removing step). The resin pattern may be removed before or after Step 5a or 5b, but preferably before Step 5a or 5b.
A method for removing the remaining resin pattern c' is not particularly limited, but a method of removing by chemical treatment is mentioned, and a method of removing using a removing liquid is preferable.
As a method for removing the resin pattern c', the substrate having the remaining resin pattern c' is placed in a stirring removal liquid whose liquid temperature is preferably 30°C to 80°C, more preferably 40°C to 80°C. A method of immersing for minutes to 30 minutes can be mentioned.

Examples of the remover include a remover obtained by dissolving an inorganic alkaline component or an organic alkaline component in water, dimethylsulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Organic alkaline components include primary amine compounds, secondary amine compounds, tertiary amine compounds and quaternary ammonium salt compounds.
Alternatively, it may be removed by a known method such as a spray method, a shower method, or a paddle method using a remover.

<Other processes>
The method for manufacturing a substrate having a conductive pattern according to the present disclosure may include arbitrary steps (other steps) other than the steps described above. Examples include, but are not limited to, the following steps.
In addition, the exposure step, development step, and other steps applicable to the method for manufacturing a substrate having a conductive pattern according to the present disclosure include the steps described in paragraphs 0035 to 0051 of JP-A-2006-23696. .
Furthermore, other steps include, for example, a step of reducing the visible light reflectance described in paragraph 0172 of WO 2019/022089, and a new step on the insulating film described in paragraph 0172 of WO 2019/022089. Examples include a step of forming a conductive layer, but the present invention is not limited to these steps.

- Step of reducing visible light reflectance -
A method of manufacturing a substrate having a conductive pattern according to the present disclosure may include a step of performing a process for reducing the visible light reflectance of part or all of the conductive layer.
The treatment for reducing the visible light reflectance includes oxidation treatment. In the case of having a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing copper to form copper oxide and blackening the conductive layer.
The treatment for reducing the visible light reflectance is described in paragraphs 0017 to 0025 of JP-A-2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of JP-A-2013-206315. , the contents of which are incorporated herein.

-Step of Forming Insulating Film, Step of Forming New Conductive Layer on Surface of Insulating Film-
The method of manufacturing a substrate having a conductive pattern according to the present disclosure also preferably includes forming an insulating film on the surface of the conductive pattern, and forming a new conductive layer on the surface of the insulating film.
Through the above steps, a second electrode pattern insulated from the first electrode pattern can be formed.
The process of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be used. Alternatively, an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive material.
The step of forming a new conductive layer on the insulating film is not particularly limited. For example, a conductive photosensitive material may be used to form a new conductive layer in a desired pattern by photolithography.

A method for manufacturing a substrate having a conductive pattern according to the present disclosure uses a substrate having a plurality of conductive layers on both surfaces of the substrate, and sequentially or simultaneously applies conductive patterns to the conductive layers formed on both surfaces of the substrate. It is also preferable to form With such a configuration, it is possible to form a circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the substrate and the second conductive pattern is formed on the other surface of the substrate. It is also preferable to form the touch panel circuit wiring having such a configuration from both sides of the support by roll-to-roll.
That is, in the method for manufacturing a substrate having a conductive pattern according to the present disclosure, it is preferable to further form the conductive pattern d' on the surface of the substrate opposite to the surface on which the conductive layer a is provided.

<Application>
A substrate having a conductive pattern manufactured by the method for manufacturing a substrate having a conductive pattern according to the present disclosure can be applied to various devices. Examples of the device provided with the substrate having the conductive pattern include an input device and the like, preferably a touch panel, and more preferably a capacitive touch panel. Further, the input device can be applied to display devices such as an organic electroluminescence display device and a liquid crystal display device.
Moreover, the substrate having a conductive pattern manufactured by the method for manufacturing a substrate having a conductive pattern according to the present disclosure can be suitably applied to a flexible display device, particularly a flexible touch panel.

<Photosensitive transfer material>
The photosensitive transfer material used in the method for manufacturing a substrate having a conductive pattern according to the present disclosure has a temporary support and a transfer layer including a photosensitive resin layer (forming the photosensitive resin layer c). is preferable, and it is more preferable to have a temporary support, a transfer layer containing a photosensitive resin layer, and a protective film in this order.
In addition, the photosensitive transfer material used in the present disclosure may have other layers between the temporary support and the photosensitive resin layer, between the photosensitive resin layer and the protective film, and the like.
Furthermore, the photosensitive transfer material used in the present disclosure preferably further has a thermoplastic resin layer and a water-soluble resin layer between the temporary support and the photosensitive resin layer.
Furthermore, the transfer layer preferably further includes a thermoplastic resin layer and a water-soluble resin layer.
The photosensitive transfer material used in the present disclosure is preferably a roll-shaped photosensitive transfer material from the viewpoint of exhibiting the effects of the present disclosure more effectively.

Examples of embodiments of the photosensitive transfer material used in the present disclosure are shown below, but are not limited thereto.
(1) "Temporary support/photosensitive resin layer/refractive index adjusting layer/protective film"
(2) "Temporary support/photosensitive resin layer/protective film"
(3) "Temporary support/water-soluble resin layer/photosensitive resin layer/protective film"
(4) "Temporary support/thermoplastic resin layer/water-soluble resin layer/photosensitive resin layer/protective film"
In each of the above configurations, the photosensitive resin layer may be a positive photosensitive resin layer or a negative photosensitive resin layer, preferably a negative photosensitive resin layer. It is also preferable that the photosensitive resin layer is a colored resin layer.
Among them, the configurations of (2) to (4) described above are preferable as the configuration of the photosensitive transfer material.

In the photosensitive transfer material, in the case of a configuration in which another layer is further provided on the side opposite to the temporary support side of the photosensitive resin layer, the sum of the other layers arranged on the side opposite to the temporary support side of the photosensitive resin layer The thickness is preferably 0.1% to 30%, more preferably 0.1% to 20%, of the layer thickness of the photosensitive resin layer.

The photosensitive transfer material used in the present disclosure will be described below by giving an example of a specific embodiment.

An example of the photosensitive transfer material will be described below.
The photosensitive transfer material 20 shown in FIG. have in order.
Further, the photosensitive transfer material 20 shown in FIG. 1 has a form in which the thermoplastic resin layer 13 and the water-soluble resin layer 15 are arranged, but the thermoplastic resin layer 13 and the water-soluble resin layer 15 may not be arranged. .
Each element constituting the photosensitive transfer material will be described below.

[Temporary support]
The photosensitive transfer material used in the present disclosure preferably has a temporary support.
The temporary support is a support that supports the photosensitive resin layer or the laminate containing the photosensitive resin layer and that can be peeled off.

The temporary support preferably has light transmittance from the viewpoint that the photosensitive resin layer can be exposed through the temporary support when the photosensitive resin layer is pattern-exposed. In this specification, "having light transmittance" means having a transmittance of 50% or more for light having a wavelength used for pattern exposure.
From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the temporary support preferably has a light transmittance of 60% or more, more preferably 70% or more, at a wavelength (more preferably a wavelength of 365 nm) used for pattern exposure. is more preferable.
The transmittance of a layer included in a photosensitive transfer material is defined as the intensity of the light emitted through the layer relative to the intensity of the incident light when the light is incident in the direction perpendicular to the main surface of the layer (thickness direction). It is the ratio of the intensity of incident light, and is measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.

Materials constituting the temporary support include, for example, glass substrates, resin films, and paper, with resin films being preferred from the viewpoints of strength, flexibility, and light transmittance.
Resin films include polyethylene terephthalate (PET) films, cellulose triacetate films, polystyrene films and polycarbonate films. Among them, a PET film is preferable, and a biaxially stretched PET film is more preferable.

The thickness (layer thickness) of the temporary support is not particularly limited. Selection may be made according to the material.
The thickness of the temporary support is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 50 μm, still more preferably in the range of 10 μm to 20 μm, even more preferably in the range of 10 μm to 16 μm, from the viewpoint of ease of handling and versatility. Especially preferred.
In addition, the thickness of the temporary support is preferably 50 μm or less, more preferably 25 μm or less, and more preferably 20 μm or less from the viewpoint of defect suppression, resolution and linearity of the resin pattern. More preferably, it is particularly preferably 16 μm or less.

Moreover, it is preferable that the film used as the temporary support does not have deformation such as wrinkles, flaws, or defects.
From the viewpoint of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, the number of fine particles, foreign matter, defects, deposits, etc. contained in the temporary support is preferably as small as possible. The number of fine particles, foreign substances, and defects with a diameter of 1 μm or more is preferably 50/10 mm ² or less, more preferably 10/10 mm ² or less, and even more preferably 3/10 mm ² or less. , 0/10 mm ² .

The haze of the temporary support is preferably as small as possible from the viewpoints of the defect-suppressing property of the resin pattern, the resolution, and the transparency of the temporary support. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 1.5% or less, still more preferably less than 1.0%, and particularly preferably 0.5% or less.
The haze value in the present disclosure is measured by a method according to JIS K 7105:1981 using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

A layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support from the viewpoint of imparting handleability. The lubricant layer may be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer can be, for example, 0.05 μm to 0.8 μm. Further, the layer thickness of the lubricant layer can be, for example, 0.05 μm to 1.0 μm.

The arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive resin layer side is the above-mentioned photosensitive property of the temporary support from the viewpoint of transportability, defect suppression of the resin pattern, and resolution. It is preferably equal to or greater than the arithmetic mean roughness Ra of the surface on the resin layer side.
The arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive resin layer side is preferably 100 nm or less from the viewpoints of transportability, resin pattern defect suppression, and resolution. , is more preferably 50 nm or less, still more preferably 20 nm or less, and particularly preferably 10 nm or less.
The arithmetic mean roughness Ra of the surface of the temporary support on the side of the photosensitive resin layer is preferably 100 nm or less from the viewpoints of peelability of the temporary support, defect suppression of the resin pattern, and resolution. , is more preferably 50 nm or less, still more preferably 20 nm or less, and particularly preferably 10 nm or less.
In addition, the value of the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive resin layer side-the arithmetic mean roughness Ra of the surface of the temporary support facing the photosensitive resin layer is the transportability, From the viewpoints of resin pattern defect suppression and resolution, the thickness is preferably 0 nm to 10 nm, more preferably 0 nm to 5 nm.

The arithmetic mean roughness Ra of the surface of the temporary support or protective film in the present disclosure shall be measured by the following method.
Using a three-dimensional optical profiler (New View 7300, manufactured by Zygo), the surface of the temporary support or protective film is measured under the following conditions to obtain the surface profile of the film.
As measurement/analysis software, Microscope Application of MetroPro ver 8.3.2 is used. Next, a Surface Map screen is displayed using the analysis software, and histogram data is obtained on the Surface Map screen. From the obtained histogram data, the arithmetic average roughness is calculated to obtain the Ra value of the surface of the temporary support or protective film.
When the temporary support or protective film is attached to a photosensitive resin layer or the like, the temporary support or protective film may be peeled off from the photosensitive resin layer and the Ra value of the peeled surface may be measured.

The peeling force of the temporary support, specifically, the peeling force between the temporary support and the photosensitive resin layer or the thermoplastic resin layer is , From the viewpoint of suppressing peeling of the temporary support due to adhesion between the vertically stacked laminate and the laminate, it is preferably 0.5 mN / mm or more, and 0.5 mN / mm to 2.0 mN / mm is more preferable.

The peel strength of the temporary support in the present disclosure shall be measured as follows.
A copper layer with a thickness of 200 nm is formed on a polyethylene terephthalate (PET) film with a thickness of 100 μm by a sputtering method to prepare a PET substrate with a copper layer.
The protective film is peeled off from the prepared photosensitive transfer material, and the material is laminated on the PET substrate with the copper layer under the lamination conditions of laminating roll temperature of 100° C., linear pressure of 0.6 MPa, and linear speed (laminating speed) of 1.0 m/min. Next, after pasting a tape (PRINTACK manufactured by Nitto Denko Corporation) on the surface of the temporary support, a laminate having at least a temporary support and a photosensitive resin layer on a PET substrate with a copper layer is 70 mm × 10 mm. Cut into pieces to make samples. The PET substrate side of the sample is fixed on the sample stage.
Using a tensile compression tester (manufactured by Imada Seisakusho Co., Ltd., SV-55), the tape is pulled at 5.5 mm / sec in the direction of 180 degrees, and the photosensitive resin layer or thermoplastic resin layer and the temporary support and measure the force (peeling force) required for peeling and adhesion.

Preferred embodiments of the temporary support include, for example, paragraphs 0017 to 0018 of JP-A-2014-85643, paragraphs 0019-0026 of JP-A-2016-27363, and paragraphs 0041 to 0057 of WO 2012/081680. , paragraphs 0029 to 0040 of WO 2018/179370 and paragraphs 0012 to 0032 of JP 2019-101405, and the contents of these publications are incorporated herein.

[Photosensitive resin layer]
The photosensitive transfer material used in the present disclosure has a photosensitive resin layer.
The photosensitive resin layer may be a positive photosensitive resin layer or a negative photosensitive resin layer, preferably a negative photosensitive resin layer.
The negative type photosensitive resin layer preferably contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. Based on the total weight of the photosensitive resin layer, the alkali-soluble resin: 10% to 90% by weight. ethylenically unsaturated compound: 5% to 70% by mass; and photopolymerization initiator: 0.01% to 20% by mass.
The positive photosensitive resin layer is not limited, and a known positive photosensitive resin layer can be used. The positive photosensitive resin layer preferably contains an acid-decomposable resin, that is, a polymer having structural units having acid groups protected by acid-decomposable groups, and a photoacid generator. Moreover, the positive photosensitive resin layer preferably contains a resin having a structural unit having a phenolic hydroxyl group and a quinonediazide compound.
Further, the positive photosensitive resin layer is more preferably a chemically amplified positive photosensitive resin layer containing a polymer having a structural unit having an acid group protected by an acid-decomposable group, and a photoacid generator. preferable.
Each component will be described in order below. In addition, when simply calling it a "photosensitive resin layer", both a positive photosensitive resin layer and a negative photosensitive resin layer shall be said.

<<polymerizable compound>>
The negative photosensitive resin layer preferably contains a polymerizable compound. As used herein, the term "polymerizable compound" means a compound that polymerizes under the action of a photopolymerization initiator, which will be described later, and which is different from the alkali-soluble resin, which will be described later.

The polymerizable group possessed by the polymerizable compound is not particularly limited as long as it is a group involved in the polymerization reaction. For example, it has an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group and a maleimide group. groups; and groups having cationic polymerizable groups such as epoxy groups and oxetane groups.
As the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.
Moreover, as a polymerizable compound, it is preferable that an ethylenically unsaturated compound is included, and it is more preferable that a (meth)acrylate compound is included.

From the viewpoint of resolution and pattern formation, the negative photosensitive resin layer preferably contains a bifunctional or higher polymerizable compound (polyfunctional polymerizable compound), and contains a trifunctional or higher polymerizable compound. is more preferable.
Here, the bifunctional or higher polymerizable compound means a compound having two or more polymerizable groups in one molecule.
Moreover, the number of polymerizable groups in one molecule of the polymerizable compound is preferably 6 or less from the viewpoint of excellent resolution and releasability.

The negative photosensitive resin layer preferably contains a bifunctional or trifunctional ethylenically unsaturated compound in that the photosensitive resin layer has a better balance between the photosensitivity, resolution, and releasability. More preferably, it contains a polyunsaturated compound.
In the negative photosensitive resin layer, the content of the bifunctional or trifunctional ethylenically unsaturated compound with respect to the total content of the ethylenically unsaturated compounds is preferably 60% by mass or more, and 70% by mass, from the viewpoint of excellent peelability. It is more preferably more than 90 mass % or more. The upper limit is not particularly limited, and may be 100% by mass. That is, all the ethylenically unsaturated compounds contained in the negative photosensitive resin layer may be bifunctional ethylenically unsaturated compounds.

From the viewpoint of resolution and pattern formability, the negative photosensitive resin layer preferably contains a polymerizable compound having a polyalkylene oxide structure, and more preferably contains a polymerizable compound having a polyethylene oxide structure. .
Preferred examples of the polymerizable compound having a polyalkylene oxide structure include polyalkylene glycol di(meth)acrylate, which will be described later.

-Ethylenically unsaturated compound B1-
The negative photosensitive resin layer preferably contains an ethylenically unsaturated compound B1 having an aromatic ring and two ethylenically unsaturated groups. The ethylenically unsaturated compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the ethylenically unsaturated compounds described above.

In the negative photosensitive resin layer, the mass ratio of the content of the ethylenically unsaturated compound B1 to the content of the ethylenically unsaturated compound is preferably 40% by mass or more from the viewpoint of better resolution. It is more preferably 50% by mass or more, still more preferably 55% by mass or more, and particularly preferably 60% by mass or more. Although the upper limit is not particularly limited, it is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less, from the viewpoint of releasability.

Examples of the aromatic ring of the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring. Aromatic heterocycles and condensed rings thereof are included, with aromatic hydrocarbon rings being preferred, and benzene rings being more preferred. In addition, the said aromatic ring may have a substituent.
Ethylenically unsaturated compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

The ethylenically unsaturated compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing swelling of the negative photosensitive resin layer due to the developer.
The bisphenol structure includes, for example, a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane) and a bisphenol derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane). The F structure and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane) can be mentioned, with the bisphenol A structure being preferred.

Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include compounds having a bisphenol structure and two ethylenically unsaturated groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. .
Both ends of the bisphenol structure and the two ethylenically unsaturated groups may be directly bonded or bonded via one or more alkyleneoxy groups. The alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule.
The ethylenically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in this publication are incorporated herein.

The ethylenically unsaturated compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, more preferably 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane.
Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical ( Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, Shin-Nakamura Chemical Industry ( Ltd.), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadeca Ethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.) ), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

A compound represented by the following formula (Bis) can be used as the ethylenically unsaturated compound B1.

In formula (Bis), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ and n ₃ are each independently , an integer of 1 to 39, n ₁ + n ₃ is an integer of 2 to 40, n ₂ and n ₄ are each independently an integer of 0 to 29, and n ₂ + n ₄ is 0 to It is an integer of 30, and the arrangement of repeating units of -(AO)- and -(B-O)- may be random or block. In the case of a block, either -(AO)- or -(B-O)- may be on the bisphenol structure side.
In one aspect, n ₁ +n ₂ +n ₃ +n ₄ is preferably an integer of 2-20, more preferably an integer of 2-16, and even more preferably an integer of 4-12. Also, n ₂ +n ₄ is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 2, and particularly preferably 0.

Ethylenically unsaturated compound B1 may be used alone or in combination of two or more.
The content of the ethylenically unsaturated compound B1 in the negative photosensitive resin layer is preferably 10% by mass or more, and 20% by mass, based on the total mass of the negative photosensitive resin layer from the viewpoint of better resolution. % or more is more preferable. Although the upper limit is not particularly limited, it is preferably 70% by mass or less, and 60% by mass or less from the viewpoint of transferability and edge fusion (a phenomenon in which components in the negative photosensitive resin layer ooze out from the edge of the photosensitive transfer material). is more preferred.

The negative photosensitive resin layer may contain an ethylenically unsaturated compound other than the ethylenically unsaturated compound B1 described above.
Ethylenically unsaturated compounds other than the ethylenically unsaturated compound B1 are not particularly limited and can be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound.

Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate. , and phenoxyethyl (meth)acrylate.

Examples of bifunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate. be done.
Alkylene glycol di(meth)acrylates include, for example, tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., Ltd. ), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd. ), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.
Polyalkylene glycol di(meth)acrylates include, for example, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.
Urethane di(meth)acrylates include, for example, propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Commercially available products include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.). mentioned.

Examples of trifunctional or higher ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri(meth) Acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof.
Here, "(tri/tetra/penta/hexa) (meth)acrylate" is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. , "(tri/tetra)(meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate. In one aspect, the negative photosensitive resin layer preferably contains the above-described ethylenically unsaturated compound B1 and a trifunctional or higher ethylenically unsaturated compound, and the above-described ethylenically unsaturated compound B1 and two or more kinds of 3 It is more preferred to include a functional or higher ethylenically unsaturated compound. In this case, the mass ratio of the ethylenically unsaturated compound B1 and the tri- or higher functional ethylenically unsaturated compound is (total mass of the ethylenically unsaturated compound B1):(total mass of the tri- or higher functional ethylenically unsaturated compound). = 1:1 to 5:1 is preferred, 1.2:1 to 4:1 is more preferred, and 1.5:1 to 3:1 is even more preferred.
In one aspect, the negative photosensitive resin layer preferably contains the ethylenically unsaturated compound B1 and two or more trifunctional ethylenically unsaturated compounds.

Examples of alkylene oxide-modified tri- or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A manufactured by Shin-Nakamura Chemical Co., Ltd. -9300-1CL, etc.), alkylene oxide-modified (meth) acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL manufactured by Daicel Allnex Co., Ltd. (registered trademark) 135, etc.), ethoxylated glycerin triacrylate (A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M- 520 (manufactured by Toagosei Co., Ltd.) and Aronix M-510 (manufactured by Toagosei Co., Ltd.).

As ethylenically unsaturated compounds other than ethylenically unsaturated compound B1, ethylenically unsaturated compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 may be used.

The ratio Mm/Mb between the ethylenically unsaturated compound content Mm and the alkali-soluble resin content Mb in the negative photosensitive resin layer is 1.0 or less from the viewpoint of resolution and linearity. is preferred, 0.9 or less is more preferred, and 0.5 or more and 0.9 or less is particularly preferred.
Moreover, the ethylenically unsaturated compound in the negative photosensitive resin layer preferably contains a (meth)acrylic compound from the viewpoint of curability and resolution.
Furthermore, from the viewpoint of curability, resolution and linearity, the ethylenically unsaturated compound in the negative photosensitive resin layer contains a (meth)acrylic compound and is contained in the negative photosensitive resin layer. ) More preferably, the content of the acrylic compound is 60% by mass or less with respect to the total mass of the acrylic compound.

The molecular weight of the ethylenically unsaturated compound containing the ethylenically unsaturated compound B1 (weight average molecular weight (Mw) when having a distribution) is preferably 200 to 3,000, more preferably 280 to 2,200, and 300 ~2,200 is more preferred.

An ethylenically unsaturated compound may be used individually by 1 type, or may use 2 or more types together.
The content of the ethylenically unsaturated compound in the negative photosensitive resin layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, based on the total mass of the negative photosensitive resin layer. 20% by mass to 50% by mass is more preferable.

<<Photoinitiator>>
The negative photosensitive resin layer preferably contains a photopolymerization initiator.
A photopolymerization initiator is a compound that initiates polymerization of an ethylenically unsaturated compound upon exposure to actinic rays such as ultraviolet rays, visible rays, and X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used.
Photopolymerization initiators include, for example, radical photopolymerization initiators and cationic photopolymerization initiators.
Among them, the photo-radical polymerization initiator is preferable for the photosensitive resin layer from the viewpoint of resolution and pattern formability.

Examples of photoradical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, photopolymerization initiators having an α-hydroxyalkylphenone structure, and acylphosphine oxide. structure, a photopolymerization initiator having an N-phenylglycine structure, and a biimidazole compound.

As the radical photopolymerization initiator, for example, polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064-0081 of JP-A-2015-14783 may be used.

Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: Midori Chemical Co., Ltd.), benzophenone, TAZ-111 (trade name: Midori Chemical Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: IGM Resins BV (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.). be done.

Examples of commercially available radical photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE01, BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE02, manufactured by BASF) , IRGACURE OXE03 (manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG , IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins B.V.), 2- Hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGM Resins B.V.), 2 -benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylpropane-1 -one (trade name: Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2- Diphenylethan-1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins B.V.) ), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins BV), oxime ester-based photopolymerization initiator (trade name: Lunar 6, DKSH Japan Co., Ltd.), 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbisimidazole (2-(2 -chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford) and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid upon receiving an actinic ray. The photocationic polymerization initiator is preferably a compound that responds to an actinic ray with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but its chemical structure is not limited. In addition, for photocationic polymerization initiators that do not directly react to actinic rays with a wavelength of 300 nm or more, if they are compounds that react to actinic rays with a wavelength of 300 nm or more and generate an acid by using them in combination with a sensitizer, the sensitizer can be used. It can be preferably used in combination with.
The photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid with a pKa of 4 or less, more preferably a photocationic polymerization initiator that generates an acid with a pKa of 3 or less, and an acid with a pKa of 2 or less. Photocationic polymerization initiators generated are particularly preferred. Although the lower limit of pKa is not particularly defined, it is preferably -10.0 or more, for example.

Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.
Ionic photocationic polymerization initiators include, for example, onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiators described in paragraphs 0114 to 0133 of JP-A-2014-85643 may be used.

Nonionic photocationic polymerization initiators include, for example, trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds. As trichloromethyl-s-triazines, diazomethane compounds and imidosulfonate compounds, compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 may be used. Further, as the oxime sulfonate compound, compounds described in paragraphs 0084 to 0088 of WO 2018/179640 may be used.

A negative photosensitive resin layer may contain a photoinitiator individually by 1 type, and may contain 2 or more types.
The content of the photopolymerization initiator in the negative photosensitive resin layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the photosensitive resin layer. 1.0% by mass or more is more preferable. Although the upper limit is not particularly limited, it is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive resin layer.

<< Alkali-soluble resin >>
The negative photosensitive resin layer preferably contains an alkali-soluble resin.
In this specification, the term “alkali-soluble” means that the solubility in 100 g of a 1 mass % aqueous solution of sodium carbonate at a liquid temperature of 22° C. is 0.1 g or more.
Alkali-soluble resins are not particularly limited, and suitable examples include known alkali-soluble resins used in etching resists.
Also, the alkali-soluble resin is preferably a binder polymer.
The alkali-soluble resin is preferably an alkali-soluble resin having an acid group.
Among them, as the alkali-soluble resin, a polymer A described later is preferable.

-Polymer A-
It is preferable that the polymer A is included as the alkali-soluble resin.
The acid value of the polymer A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, more preferably 190 mgKOH/g, from the viewpoint of better resolution by suppressing swelling of the photosensitive resin layer due to the developer. Less than is more preferred.
The lower limit of the acid value of polymer A is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH/g or more, more preferably 120 mgKOH/g or more, still more preferably 150 mgKOH/g or more, and 170 mgKOH/g or more. Especially preferred.

The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample.
In this specification, the unit is described as mgKOH/g. The acid value can be calculated, for example, from the average content of acid groups in the compound.
The acid value of the polymer A may be adjusted according to the type of structural units constituting the polymer A and the content of structural units containing an acid group.

The weight average molecular weight of polymer A is preferably from 5,000 to 500,000. A weight average molecular weight of 500,000 or less is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, a weight average molecular weight of 5,000 or more is preferable from the viewpoint of controlling the properties of development aggregates and the properties of unexposed films such as edge-fuse properties and cut-chip properties. The weight average molecular weight is more preferably 10,000 or more, even more preferably 20,000 or more, and particularly preferably 30,000 or more. Edge fuseability refers to the degree of ease with which the photosensitive resin layer protrudes from the end face of the roll when the photosensitive transfer material is wound into a roll. The cut chip property refers to the degree of easiness of chip flying when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the photosensitive resin layer or the like, it will be transferred to the mask in the subsequent exposure process or the like, resulting in defective products. The dispersity of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and 1 .0 to 3.0 is more preferable. In the present disclosure, molecular weight is a value measured using gel permeation chromatography. The degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).

The negative photosensitive resin layer contains a monomer component having an aromatic hydrocarbon group as the polymer A from the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position during exposure is shifted. is preferred. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of the monomer component having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, preferably 30% by mass or more, based on the total mass of all monomer components. It is more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more. Although the upper limit is not particularly limited, it is preferably 95% by mass or less, more preferably 85% by mass or less. In addition, the content rate of the monomer component which has an aromatic-hydrocarbon group in the case where the polymer A contains multiple types was calculated|required as a weight average value.

Examples of the monomer having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferred. In one aspect, when the monomer component having an aromatic hydrocarbon group in the polymer A is styrene, the content of the styrene monomer component is 20% by mass based on the total mass of all monomer components. It is preferably 50% by mass, more preferably 25% by mass to 45% by mass, even more preferably 30% by mass to 40% by mass, particularly 30% by mass to 35% by mass. preferable.

The aralkyl group includes a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group, and the like, and a substituted or unsubstituted benzyl group is preferred.

Phenylethyl (meth)acrylate etc. are mentioned as a monomer which has a phenylalkyl group.

Examples of benzyl group-containing monomers include benzyl group-containing (meth)acrylates such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; benzyl group-containing vinyl monomers such as vinylbenzyl chloride and vinylbenzyl Alcohol etc. are mentioned. Among them, benzyl (meth)acrylate is preferred. In one aspect, when the monomer component having an aromatic hydrocarbon group in the polymer A is benzyl (meth) acrylate, the content of the benzyl (meth) acrylate monomer component is the total of all monomer components Based on the mass, it is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, even more preferably 70% by mass to 90% by mass, 75% by mass to 90% by mass is particularly preferred.

Polymer A containing a monomer component having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group and at least one of the first monomer described later and / or the second monomer described later. is preferably obtained by polymerizing at least one of the monomers of

Polymer A containing no monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and at least More preferably, it is obtained by copolymerizing one of the monomers with at least one of the second monomers described below.

A 1st monomer is a monomer which has a carboxy group in a molecule|numerator. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferred.
The content of the first monomer in the polymer A is preferably 5% by mass to 50% by mass, based on the total mass of all monomer components, and 10% by mass to 40% by mass. is more preferable, and 15% by mass to 30% by mass is even more preferable.

The copolymerization ratio of the first monomer is preferably 10% by mass to 50% by mass based on the total mass of all monomer components. The copolymerization ratio of 10% by mass or more is preferable from the viewpoint of developing good developability and controlling edge fuse properties, more preferably 15% by mass or more, and even more preferably 20% by mass or more. . Setting the copolymerization ratio to 50% by mass or less is preferable from the viewpoint of the high resolution and groove shape of the resist pattern, and further from the viewpoint of the chemical resistance of the resist pattern. The following is more preferable, 30% by mass or less is even more preferable, and 27% by mass or less is particularly preferable.

The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and other (meth)acrylates; vinyl acetate esters of vinyl alcohol such as; and (meth)acrylonitrile. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is particularly preferred.
The content of the second monomer in the polymer A is preferably 5% by mass to 60% by mass, based on the total mass of all monomer components, and 15% by mass to 50% by mass. is more preferable, and 20% by mass to 45% by mass is even more preferable.

Containing a monomer having an aralkyl group and/or styrene as a monomer is preferable from the viewpoint of suppressing widening of line width and deterioration of resolution when the focal position during exposure is shifted. For example, a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, and the like are preferable.
In one embodiment, the polymer A contains 25% to 40% by mass of the monomer component having an aromatic hydrocarbon group, 20% to 35% by mass of the first monomer component, and the second monomer A polymer containing 30% to 45% by mass of a solid component is preferred. In another aspect, the polymer preferably contains 70% by mass to 90% by mass of the monomer component having an aromatic hydrocarbon group and 10% by mass to 25% by mass of the first monomer component. .

Polymer A may have any one of a linear structure, a branched structure, and an alicyclic structure in the side chain. Introducing a branched structure or an alicyclic structure to the side chain of the polymer A by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain. can be done. A group having an alicyclic structure may be monocyclic or polycyclic.
Specific examples of the monomer containing a group having a branched structure in the side chain include i-propyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, (meth)acrylic t-butyl acid, i-amyl (meth)acrylate, t-amyl (meth)acrylate, iso-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, t-octyl (meth)acrylate and the like. Among these, i-propyl (meth)acrylate, i-butyl (meth)acrylate, and t-butyl methacrylate are preferred, and i-propyl methacrylate and t-butyl methacrylate are more preferred.
Examples of the monomer containing a group having an alicyclic structure in the side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group, and the number of carbon atoms (number of carbon atoms) (Meth)acrylates having 5 to 20 alicyclic hydrocarbon groups are mentioned. More specific examples include (meth)acrylate (bicyclo[2.2.1]heptyl-2), (meth)acrylate-1-adamantyl, (meth)acrylate-2-adamantyl, (meth)acrylate ) 3-methyl-1-adamantyl acrylate, 3,5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyladamantyl (meth) acrylate, 3-methyl-5 (meth) acrylate -ethyl-1-adamantyl, (meth)acrylate-3,5,8-triethyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-mentanoindene-5 (meth)acrylate -yl, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy (meth)acrylate -2,6,6-trimethyl-bicyclo[3.1.1]heptyl, (meth)acrylate-3,7,7-trimethyl-4-hydroxybicyclo[4.1.0]heptyl, (meth)acryl acid (nor)bornyl, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate and the like. Among these (meth)acrylic esters, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, -1-adamantyl (meth)acrylate, (meth)acrylate - 2-adamantyl, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, Isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are particularly preferred.

Polymer A can be used singly or in combination of two or more. When two or more types are mixed and used, two types of polymer A containing a monomer component having an aromatic hydrocarbon group are mixed and used, or a monomer component having an aromatic hydrocarbon group is used. It is preferable to use a mixture of the polymer A containing the aromatic hydrocarbon group and the polymer A containing no monomer component having an aromatic hydrocarbon group. In the latter case, the use ratio of the polymer A containing a monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more, preferably 70% by mass or more, based on the total amount of the polymer A. is more preferably 80% by mass or more, and more preferably 90% by mass or more.

Synthesis of polymer A is carried out by adding a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution obtained by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol. is preferably added in an appropriate amount and heated and stirred. In some cases, the synthesis is performed while part of the mixture is added dropwise to the reaction solution. After completion of the reaction, a solvent may be further added to adjust the desired concentration. As a means of synthesis, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The glass transition temperature Tg of the polymer A is preferably 30°C or higher and 135°C or lower. By using the polymer A having a Tg of 135° C. or lower in the photosensitive resin layer, thickening of the line width and degradation of resolution when the focal point shifts during exposure can be suppressed. From this point of view, the Tg of polymer A is more preferably 130° C. or lower, still more preferably 120° C. or lower, and particularly preferably 110° C. or lower. Moreover, it is preferable to use the polymer A having a Tg of 30° C. or more from the viewpoint of improving the edge fuse resistance. From this point of view, the Tg of the polymer A is more preferably 40° C. or higher, still more preferably 50° C. or higher, particularly preferably 60° C. or higher, and most preferably 70° C. or higher. .

The negative photosensitive resin layer may contain resins other than alkali-soluble resins.
Resins other than alkali-soluble resins include acrylic resins, styrene-acrylic copolymers (with a styrene content of 40% by mass or less), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, and epoxy resins. Resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.

Alkali-soluble resins may be used singly or in combination of two or more.
The ratio of the alkali-soluble resin to the total mass of the negative photosensitive resin layer is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and still more preferably 40% by mass. % to 60% by mass. From the viewpoint of controlling the development time, it is preferable to set the ratio of the alkali-soluble resin to 90% by mass or less with respect to the negative photosensitive resin layer. On the other hand, it is preferable from the viewpoint of improving the edge fuse resistance that the ratio of the alkali-soluble resin to the negative photosensitive resin layer is 10% by mass or more.

<<Compound having lone pair of electrons>>
From the viewpoint of adhesion to the conductive layer, the photosensitive resin layer preferably contains a compound having a lone pair of electrons.
The compound having a lone pair of electrons is preferably a compound having at least a nitrogen atom, an oxygen atom, or a sulfur atom from the viewpoint of adhesion to the conductive layer, and is a heterocyclic compound, a thiol compound, or a disulfide compound. is more preferred, a heterocyclic compound is even more preferred, and a nitrogen-containing heterocyclic compound is particularly preferred.
As the compound having a lone pair of electrons, the compounds exemplified for the compound e described above are preferably exemplified.

The photosensitive resin layer may contain one kind of compound having a lone pair of electrons, or may contain two or more kinds thereof.
The content of the compound having an unshared electron pair is preferably 0.01% by mass to 20% by mass, based on the total mass of the photosensitive resin layer, from the viewpoint of adhesion with the conductive layer, and 0.1% by mass. It is more preferably from 0.3% to 8% by mass, particularly preferably from 0.5% to 5% by mass.

<<Dye>>
The photosensitive resin layer preferably contains a dye from the viewpoint of the visibility of the exposed and unexposed areas, the visibility of the pattern after development, and the resolution. It is more preferable to contain a dye whose absorption wavelength is 450 nm or more and whose maximum absorption wavelength is changed by an acid, a base, or a radical (also simply referred to as "dye N"). When the dye N is contained, although the detailed mechanism is unknown, the adhesion to the adjacent layers (for example, the temporary support and the substrate) is improved and the resolution is improved.

As used herein, the term "the maximum absorption wavelength of a dye changes with an acid, a base, or a radical" means that the dye in a colored state is decolored by an acid, a base, or a radical, the dye in a decolored state is an acid, It may mean either a mode in which a color is developed by a base or a radical, or a mode in which a dye in a coloring state changes to a coloring state of another hue.
Specifically, the dye N may be a compound that changes from a decolored state to develop color upon exposure, or a compound that changes from a colored state to decolor upon exposure. In this case, it may be a dye whose coloring or decoloring state is changed by the action of an acid, a base, or a radical generated in the photosensitive resin layer by exposure, and the state in the photosensitive resin layer by the acid, the base, or the radical. It may also be a dye that changes its coloring or decoloring state with a change in pH (eg, pH). Moreover, it may be a dye that changes its coloring or decoloring state by being directly stimulated by an acid, a base, or a radical without being exposed to light.

Among them, from the viewpoint of visibility and resolution of exposed and unexposed areas, the dye N is preferably a dye whose maximum absorption wavelength is changed by acid or radicals, more preferably a dye whose maximum absorption wavelength is changed by radicals.
From the viewpoint of visibility and resolution of exposed and unexposed areas, the photosensitive resin layer may contain both a dye whose maximum absorption wavelength is changed by radicals as dye N and a radical photopolymerization initiator. preferable.
From the viewpoint of the visibility of the exposed and unexposed areas, the dye N is preferably a dye that develops color with an acid, a base, or a radical.

As an example of the coloring mechanism of the dye N in the present disclosure, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive resin layer, and photoradical polymerization is performed after exposure. Radical-reactive dyes, acid-reactive dyes, or base-reactive dyes (for example, leuco dyes) develop colors with radicals, acids, or bases generated from an initiator, a photocationic polymerization initiator, or a photobase generator.

From the viewpoint of the visibility of the exposed and unexposed areas, the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 nm to 780 nm during color development, more preferably 550 nm to 700 nm, and 550 nm. ~650 nm is more preferred.

The maximum absorption wavelength of Dye N is measured in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an air atmosphere. It is obtained by measuring the spectrum and detecting the wavelength (maximum absorption wavelength) at which the intensity of light is minimum in the above wavelength range.

Examples of dyes that develop or decolorize upon exposure include leuco compounds.
Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.
As the dye N, a leuco compound is preferable from the viewpoint of the visibility of the exposed area and the non-exposed area.

Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluoran dyes), and diarylmethane skeletons. a leuco compound (diarylmethane dye), a leuco compound having a rhodamine lactam skeleton (rhodamine lactam dye), a leuco compound having an indolylphthalide skeleton (indolylphthalide dye), and a leuco auramine skeleton leuco compounds (leuco auramine dyes) having
Among them, triarylmethane-based dyes or fluoran-based dyes are preferable, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluoran-based dyes are more preferable.

The leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring from the viewpoint of the visibility of the exposed area and the non-exposed area. As a result, the lactone ring, sultine ring, or sultone ring of the leuco compound is reacted with a radical generated from a radical photopolymerization initiator or an acid generated from a photocationic polymerization initiator to change the leuco compound into a ring-closed state. It can be decolored, or it can be colored by changing the leuco compound into a ring-opened state. The leuco compound is preferably a compound that has a lactone ring, a sultine ring or a sultone ring and develops a color when the lactone ring, sultine ring or sultone ring is opened by a radical or an acid. A compound that develops color by ring-opening of the lactone ring is more preferred.

Examples of dye N include the following dyes and leuco compounds.
Specific examples of dyes among dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, methanil yellow, thymolsulfophtalein, xylenol blue, methyl Orange, Paramethyl Red, Congo Fred, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsin, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (protective Tsuchiya Chemical Industry Co., Ltd.), Oil Blue #603 (Orient Chemical Industry Co., Ltd.), Oil Pink #312 (Orient Chemical Industry Co., Ltd.), Oil Red 5B (Orient Chemical Industry Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industry Co., Ltd.) ), Spiron Red BEH Special (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxy Anilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylamino phenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of the leuco compound of the dye N include p,p′,p″-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p -toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methyl amino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7 -xyridinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N ,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino)-7-benzylaminofluorane, 3- (N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6 -methyl-7-xyridinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl- 2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethyl aminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-( 1-ethyl-2-methylindol-3-yl)phthalide and 3′,6′-bis(diphenylamino)spiroisobenzofuran-1(3H),9′-[9H]xanthen-3-one be done.

Dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and is a dye that develops color by radicals. is more preferable.
Preferred dyes N are leuco crystal violet, crystal violet lactone, brilliant green, or victoria pure blue-naphthalene sulfonate.

A dye may be used individually by 1 type, or may use 2 or more types.
The content of the dye is preferably 0.1% by mass or more based on the total mass of the photosensitive resin layer, from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. , more preferably 0.1% by mass to 10% by mass, still more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass.
In addition, the content of the dye N is 0.1% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of the visibility of the exposed area and the non-exposed area, the pattern visibility after development, and the resolution. The above is preferable, 0.1% by mass to 10% by mass is more preferable, 0.1% by mass to 5% by mass is still more preferable, and 0.1% by mass to 1% by mass is particularly preferable.

The content of the dye N means the content of the dye when all the dyes N contained in the photosensitive resin layer are in a colored state. A method for quantifying the content of dye N will be described below using a dye that develops color by radicals as an example.
Two solutions are prepared by dissolving 0.001 g or 0.01 g of dye in 100 mL of methyl ethyl ketone. A radical photopolymerization initiator Irgacure OXE01 (trade name, BASF Japan Co., Ltd.) is added to each of the obtained solutions, and radicals are generated by irradiation with light of 365 nm to make all the dyes develop colors. After that, the absorbance of each solution having a liquid temperature of 25° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an air atmosphere to create a calibration curve.
Next, the absorbance of the solution in which all the dyes are developed is measured in the same manner as described above except that 3 g of the photosensitive resin layer is dissolved in methyl ethyl ketone instead of the dyes. From the absorbance of the obtained solution containing the photosensitive resin layer, the content of the dye contained in the photosensitive resin layer is calculated based on the calibration curve.

<<Thermal crosslinkable compound>>
The photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as a polymerizable compound, but as a thermally crosslinkable compound.
Thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds. Among them, a blocked isocyanate compound is preferable from the viewpoint of the strength of the cured film to be obtained and the adhesiveness of the uncured film to be obtained.
Since the blocked isocyanate compound reacts with the hydroxy group and the carboxy group, for example, when the resin and/or the polymerizable compound has at least one of the hydroxy group and the carboxy group, the hydrophilicity of the formed film is lowered. There is a tendency for the function to be enhanced when a film obtained by curing a photosensitive resin layer is used as a protective film.
The blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, more preferably 130°C to 150°C.
The dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter".
As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.

Blocking agents having a dissociation temperature of 100° C. to 160° C. include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds. (Compounds having a structure represented by -C(=N-OH)- in the molecule such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime).
Among these, the blocking agent having a dissociation temperature of 100° C. to 160° C. preferably contains an oxime compound, for example, from the viewpoint of storage stability.

The blocked isocyanate compound preferably has an isocyanurate structure from the viewpoint of, for example, improving the brittleness of the film and improving the adhesion to the transferred material.
A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by converting hexamethylene diisocyanate into an isocyanurate for protection.
Among the blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent tend to have a dissociation temperature within a preferred range and can reduce development residues more easily than compounds having no oxime structure. This is preferable from the viewpoint of ease of use.

The blocked isocyanate compound may have a polymerizable group.
The polymerizable group is not particularly limited, and any known polymerizable group can be used, and a radically polymerizable group is preferred.
Polymerizable groups include groups having ethylenically unsaturated groups such as (meth)acryloxy groups, (meth)acrylamide groups and styryl groups, and epoxy groups such as glycidyl groups.
Among them, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and still more preferably an acryloxy group.

A commercial item can be used as a blocked isocyanate compound.
Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by Showa Denko K.K.), block type Duranate series (eg, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).
Moreover, the compound of the following structure can also be used as a blocked isocyanate compound.

The thermally crosslinkable compounds may be used singly or in combination of two or more.
When the photosensitive resin layer contains a heat-crosslinkable compound, the content of the heat-crosslinkable compound is preferably 1% by mass to 50% by mass, and 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer. is more preferred.

<<Polymer having a structural unit having an acid group protected by an acid-decomposable group>>
The positive photosensitive resin layer comprises a polymer (hereinafter referred to as "polymer X") having a structural unit having an acid group protected by an acid-decomposable group (hereinafter sometimes referred to as "structural unit A"). There is.) is preferably included. The positive photosensitive resin layer may contain a single type of polymer X, or may contain two or more types of polymer X.

In the polymer X, acid groups protected by acid-decomposable groups are converted to acid groups through a deprotection reaction by the action of a catalytic amount of an acidic substance (eg, acid) generated by exposure. The formation of acid groups in the polymer X increases the solubility of the positive photosensitive resin layer in the developer.

The polymer X is preferably an addition polymerization type polymer, more preferably a polymer having a structural unit derived from (meth)acrylic acid or its ester.

-Structural Unit Having an Acid Group Protected with an Acid-Decomposable Group-
Polymer X preferably has a structural unit (structural unit A) having an acid group protected with an acid-decomposable group. By having the structural unit A in the polymer X, the sensitivity of the positive photosensitive resin layer can be improved.

The acid group is not limited, and known acid groups can be used. The acid group is preferably a carboxy group or a phenolic hydroxyl group.

The acid-decomposable group includes, for example, a group that is relatively easily decomposed by acid and a group that is relatively difficult to be decomposed by acid. Groups that are relatively easily decomposed by acids include, for example, acetal-type protecting groups (eg, 1-alkoxyalkyl groups, tetrahydropyranyl groups, and tetrahydrofuranyl groups). Groups that are relatively difficult to decompose with acids include, for example, tertiary alkyl groups (eg, tert-butyl group) and tertiary alkyloxycarbonyl groups (eg, tert-butyloxycarbonyl group). Among the above, the acid-decomposable group is preferably an acetal-type protecting group.

The molecular weight of the acid-decomposable group is preferably 300 or less from the viewpoint of suppressing variations in the line width of the resin pattern.

From the viewpoint of sensitivity and resolution, the structural unit A is preferably a structural unit represented by the following formula A1, a structural unit represented by the formula A2, or a structural unit represented by the formula A3. It is more preferable that it is a structural unit represented by. The structural unit represented by formula A3 is a structural unit having a carboxyl group protected with an acetal-type acid-labile group.

In Formula A1, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ¹¹ and R ¹² is an alkyl group or an aryl group, and R ¹³ is represents an alkyl group or an aryl group; R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether; R ¹⁴ represents a hydrogen atom or a methyl ^group ; represents a bond or a divalent linking group, R ¹⁵ represents a substituent, and n represents an integer of 0-4.

In Formula A2, R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ²¹ and R ²² is an alkyl group or an aryl group, and R ²³ is represents an alkyl group or an aryl group, R ²¹ or R ²² and R ²³ may be linked to form a cyclic ether, and R ²⁴ each independently represents a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, alkenyl group, aryl group, aralkyl group, alkoxycarbonyl group, hydroxyalkyl group, arylcarbonyl group, aryloxycarbonyl group, or cycloalkyl group; m represents an integer of 0 to 3;

In Formula A3, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group , or represents an aryl group, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, X ⁰ represents a single bond, or represents an arylene group.

In Formula A3, when R ³¹ or R ³² is an alkyl group, it is preferably an alkyl group having 1 to 10 carbon atoms.
In formula A3, when R ³¹ or R ³² is an aryl group, a phenyl group is preferred.
In formula A3, R ³¹ and R ³² are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In formula A3, R ³³ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
In formula A3, the alkyl group and aryl group represented by R ³¹ to R ³³ may have a substituent.
In Formula A3, R ³¹ or R ³² and R ³³ are preferably linked to form a cyclic ether. The number of ring members of the cyclic ether is preferably 5 or 6, more preferably 5.
In formula A3, X ⁰ is preferably a single bond. The arylene group may have a substituent.
In formula A3, R ³⁴ is preferably a hydrogen atom from the viewpoint that the glass transition temperature (Tg) of polymer X can be made lower.

The content of structural units in which R ³⁴ in formula A3 is a hydrogen atom is preferably 20% by mass or more with respect to the total mass of structural units A contained in polymer X. The content of structural units in which R ³⁴ in formula A3 is a hydrogen atom in structural unit A is confirmed by the intensity ratio of peak intensities calculated by a conventional method from ¹³ C-nuclear magnetic resonance spectroscopy (NMR) measurement. can be done.

Preferred embodiments of formulas A1 to A3 can be referred to paragraphs 0044 to 0058 of WO 2018/179640.

In the formulas A1 to A3, the acid-decomposable group is preferably a group having a cyclic structure from the viewpoint of sensitivity, more preferably a group having a tetrahydrofuran ring structure or a tetrahydropyran ring structure, and a tetrahydrofuran ring structure. group is more preferred, and a tetrahydrofuranyl group is particularly preferred.

The polymer X may have a single structural unit A, or may have two or more structural units A.

The content of the structural unit A is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 50% by mass, and 20% by mass to 40% by mass, based on the total mass of the polymer X. % by weight is particularly preferred. When the content of the structural unit A is within the above range, the resolution is further improved. When the polymer X contains two or more structural units A, the content of the structural units A represents the total content of the two or more structural units A. The content of the structural unit A can be confirmed by the ratio of peak intensities calculated by a conventional method from ¹³ C-NMR measurement.

- Structural Unit Having an Acid Group -
The polymer X may have a structural unit having an acid group (hereinafter sometimes referred to as "structural unit B").

Structural unit B is a structural unit having an acid group that is not protected by an acid-decomposable group, that is, an acid group that does not have a protective group. Since the polymer X has the structural unit B, the sensitivity during pattern formation is improved. Moreover, since it becomes easy to melt|dissolve in an alkaline developer in the developing process after exposure, shortening of development time can be aimed at.

The acid group in the structural unit B means a proton-dissociating group with a pKa of 12 or less. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, more preferably 6 or less. Also, the pKa of the acid group is preferably -5 or higher.

Acid groups include, for example, carboxy groups, sulfonamide groups, phosphonic acid groups, sulfo groups, phenolic hydroxyl groups, and sulfonylimide groups. The acid group is preferably a carboxy group or a phenolic hydroxyl group, more preferably a carboxy group.

The polymer X may have a single structural unit B, or may have two or more structural units B.

The content of the structural unit B is preferably 0.01% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, relative to the total mass of the polymer X. .1% to 5% by weight is particularly preferred. When the content of the structural unit B is within the above range, the resolution becomes better. When the polymer X has two or more types of structural units B, the content of the structural units B indicates the total content of the two or more types of structural units B. The content of the structural unit B can be confirmed by an intensity ratio of peak intensities calculated by a conventional method from ¹³ C-NMR measurement.

-Other structural units-
Polymer X preferably has other structural units (hereinafter sometimes referred to as "structural unit C") other than structural unit A and structural unit B described above. Various properties of the polymer X can be adjusted by adjusting at least one of the type and content of the structural unit C. Since the polymer X has the structural unit C, the glass transition temperature, acid value, and hydrophilicity/hydrophobicity of the polymer X can be easily adjusted.

Examples of monomers forming the structural unit C include styrenes, (meth)acrylic acid alkyl esters, (meth)acrylic acid cyclic alkyl esters, (meth)acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, and bicyclounsaturated compounds. , maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated dicarboxylic acid anhydrides.

The monomer forming the structural unit C is preferably a (meth)acrylic acid alkyl ester from the viewpoint of adhesion to the substrate, and is a (meth)acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms. is more preferable. Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-(meth)acrylate. Ethylhexyl is mentioned.

Structural unit C includes styrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, methyl (meth)acrylate, ethyl (meth)acrylate, ( n-propyl meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(meth)acrylate Structural units derived from hydroxypropyl, benzyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, acrylonitrile, or ethylene glycol monoacetoacetate mono(meth)acrylate mentioned. Structural unit C also includes structural units derived from compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623.

Structural unit C preferably contains a structural unit having a basic group from the viewpoint of resolution. Basic groups include, for example, groups having a nitrogen atom. Groups having a nitrogen atom include, for example, aliphatic amino groups, aromatic amino groups, and nitrogen-containing heteroaromatic ring groups. The basic group is preferably an aliphatic amino group.

The aliphatic amino group may be a primary amino group, a secondary amino group, or a tertiary amino group, but from the viewpoint of resolution, a secondary amino group or a tertiary A tertiary amino group is preferred.

Examples of monomers that form a structural unit having a basic group include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 2,2-acrylic acid, 6,6-tetramethyl-4-piperidyl, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, methacrylate 2-( diethylamino)ethyl, 2-(dimethylamino)ethyl acrylate, 2-(diethylamino)ethyl acrylate, N-(3-dimethylamino)propyl methacrylate, N-(3-dimethylamino)propyl acrylate, N methacrylate -(3-diethylamino)propyl, N-(3-diethylamino)propyl acrylate, 2-(diisopropylamino)ethyl methacrylate, 2-morpholinoethyl methacrylate, 2-morpholinoethyl acrylate, N-[3-(dimethyl amino)propyl]acrylamide, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole, and 1-vinyl- 1,2,4-triazoles may be mentioned. Among the above, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate is preferred.

Moreover, as the structural unit C, a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton is preferable from the viewpoint of improving electrical properties. Examples of monomers forming these structural units include styrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and benzyl ( meth)acrylates. Among the above, cyclohexyl (meth)acrylate is preferred.

The polymer X may have a single structural unit C, or may have two or more structural units C.

The content of the structural unit C is preferably 90% by mass or less, more preferably 85% by mass or less, and particularly preferably 80% by mass or less, relative to the total mass of the polymer X. The content of the structural unit C is preferably 10% by mass or more, more preferably 20% by mass or more, relative to the total mass of the polymer X. When the content of the structural unit C is within the above range, the resolution and adhesion to the substrate are further improved. When the polymer X has two or more structural units C, the content of the structural units C indicates the total content of the two or more structural units C. The content of the structural unit C can be confirmed by an intensity ratio of peak intensities calculated by a conventional method from ¹³ C-NMR measurement.

Preferred examples of polymer X are shown below. However, polymer X is not limited to the following examples. In addition, the ratio of each structural unit and the weight average molecular weight in the polymer X shown below are appropriately selected in order to obtain preferable physical properties.

-Glass-transition temperature-
The glass transition temperature (Tg) of the polymer X is preferably 90°C or less, more preferably 20°C to 60°C, and particularly preferably 30°C to 50°C. When the positive photosensitive resin layer is formed using a transfer material to be described later, the transferability of the positive photosensitive resin layer can be improved by setting the glass transition temperature of the polymer X within the above range.

Examples of a method for adjusting the Tg of the polymer X within the above range include a method using the FOX formula. According to the FOX formula, for example, the Tg of the target polymer X can be adjusted based on the Tg of the homopolymer of each structural unit in the target polymer X and the mass fraction of each structural unit.

The FOX formula will be described below using a copolymer having a first structural unit and a second structural unit as an example.
The glass transition temperature of the homopolymer of the first structural unit is Tg1, the mass fraction of the first structural unit in the copolymer is W1, the glass transition temperature of the homopolymer of the second structural unit is Tg2, and the copolymer is When the mass fraction of the second structural unit in the coalescence is W2, the glass transition temperature Tg0 (unit: K) of the copolymer having the first structural unit and the second structural unit is given by the following formula. It can therefore be estimated.
FOX formula: 1/Tg0 = (W1/Tg1) + (W2/Tg2)

Also, the Tg of the polymer can be adjusted by adjusting the weight average molecular weight of the polymer.

- Acid value -
From the viewpoint of resolution, the acid value of polymer X is preferably 0 mgKOH/g to 50 mgKOH/g, more preferably 0 mgKOH/g to 20 mgKOH/g, and 0 mgKOH/g to 10 mgKOH/g. It is particularly preferred to have

The acid value of a polymer represents the mass of potassium hydroxide required to neutralize acidic components per gram of polymer. A specific measuring method will be described below. First, a measurement sample is dissolved in a mixed solvent containing tetrahydrofuran and water (volume ratio: tetrahydrofuran/water=9/1). Using a potentiometric titrator (eg, trade name: AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.), the obtained solution is subjected to neutralization titration with a 0.1 mol/L sodium hydroxide aqueous solution at 25°C. Using the inflection point of the titration pH curve as the titration end point, the acid value is calculated by the following formula.
A = 56.11 x Vs x 0.1 x f/w
A: Acid value (mgKOH/g)
Vs: Amount (mL) of 0.1 mol/L aqueous sodium hydroxide solution required for titration
f: titer of 0.1 mol/L sodium hydroxide aqueous solution w: mass (g) of measurement sample (in terms of solid content)

-Weight average molecular weight-
The weight average molecular weight (Mw) of the polymer X is preferably 60,000 or less in terms of polystyrene conversion weight average molecular weight. When the positive photosensitive resin layer is formed using a transfer material described later, the weight average molecular weight of the polymer X is 60,000 or less, so that the positive photosensitive resin layer can be formed at a low temperature (for example, 130 ° C. or less). can be transcribed.

The weight average molecular weight of polymer X is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.

The ratio of the number average molecular weight to the weight average molecular weight (dispersion degree) of the polymer X is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

The weight average molecular weight of polymer X is measured by GPC (gel permeation chromatography). Various commercially available devices can be used as the measuring device. The method for measuring the weight-average molecular weight of polymer X by GPC will be specifically described below.
HLC (registered trademark)-8220GPC (manufactured by Tosoh Corporation) is used as a measuring device.
As columns, TSKgel (registered trademark) Super HZM-M (4.6 mm ID × 15 cm, manufactured by Tosoh Corporation), Super HZ4000 (4.6 mm ID × 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mm ID × 15 cm) , manufactured by Tosoh Corporation) and Super HZ2000 (4.6 mm ID×15 cm, manufactured by Tosoh Corporation) are connected in series.
THF (tetrahydrofuran) is used as an eluent.
The measurement conditions are a sample concentration of 0.2% by mass, a flow rate of 0.35 mL/min, a sample injection volume of 10 μL, and a measurement temperature of 40°C.
A differential refractive index (RI) detector is used as the detector.
The calibration curve is "Standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", "A -2500" and 7 samples of "A-1000".

-Content-
From the viewpoint of high resolution, the content of the polymer X is preferably 50% by mass to 99.9% by mass, more preferably 70% by mass to 98% by mass, based on the total mass of the positive photosensitive resin layer. % is more preferable.

-Production method-
A method for producing the polymer X is not limited, and a known method can be used. For example, in an organic solvent, using a polymerization initiator, a monomer for forming the structural unit A, and optionally, a monomer for forming the structural unit B and a monomer for forming the structural unit C are polymerized. Polymer X can be produced by doing so. Polymer X can also be produced by a so-called polymer reaction.

<<Other polymers>>
When the positive photosensitive resin layer contains a polymer having a structural unit having an acid group-protected acid-decomposable group, in addition to the polymer having a structural unit having an acid-decomposable group-protected acid group, Furthermore, it may contain a polymer having no constitutional unit having an acid group-protected acid-decomposable group (hereinafter sometimes referred to as "another polymer").

Other polymers include, for example, polyhydroxystyrene. Commercial products of polyhydroxystyrene include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F manufactured by Sartomer, and ARUFON UC-3000 and ARUFON UC-3510 manufactured by Toagosei Co., Ltd. , ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080, and Joncryl 690, Joncryl 678, Joncryl 67, and Joncryl 586 manufactured by BASF.

The positive photosensitive resin layer may contain one type of other polymer alone, or may contain two or more types of other polymers.

When the positive photosensitive resin layer contains another polymer, the content of the other polymer is preferably 50% by mass or less, and 30% by mass or less, relative to the total mass of the polymer components. is more preferable, and 20% by mass or less is particularly preferable.

In the present disclosure, "polymer component" is a generic term for all polymers contained in the positive photosensitive resin layer. For example, when the positive photosensitive resin layer contains the polymer X and another polymer, the polymer X and the other polymer are collectively referred to as "polymer component". Compounds corresponding to cross-linking agents, dispersants, and surfactants, which will be described later, are not included in the polymer component even if they are polymer compounds.

The content of the polymer component is preferably 50% by mass to 99.9% by mass, more preferably 70% by mass to 98% by mass, based on the total mass of the positive photosensitive resin layer.

<< Alkali-soluble resin (positive type) >>
The positive photosensitive resin layer preferably contains an alkali-soluble resin, more preferably contains an alkali-soluble resin and a quinonediazide compound, and particularly preferably contains a resin having a structural unit having a phenolic hydroxyl group and a quinonediazide compound.

Alkali-soluble resins include, for example, resins having a hydroxyl group, a carboxyl group or a sulfo group in the main chain or side chain. Alkali-soluble resins include, for example, polyamide resins, polyhydroxystyrenes, derivatives of polyhydroxystyrenes, styrene-maleic anhydride copolymers, polyvinyl hydroxybenzoate, carboxy group-containing (meth)acrylic resins, and novolak resins. Preferred alkali-soluble resins include, for example, condensation polymers of m-/p-mixed cresol and formaldehyde and condensation polymers of phenol, cresol and formaldehyde.

Alkali-soluble resins include phenolic hydroxyl groups (--Ar--OH), carboxy groups (--CO ₂ H), sulfo groups (--SO ₃ H), phosphoric acid groups (--OPO ₃ H), sulfonamide groups (--SO ₂ NH—R) or substituted sulfonamide acid groups (eg, activated imide groups, —SO ₂ NHCOR, —SO ₂ NHSO ₂ R and —CONHSO ₂ R). Here, Ar represents a divalent aryl group which may have a substituent, and R represents a hydrocarbon group which may have a substituent.

A novolac resin is obtained, for example, by condensing a phenolic compound and an aldehyde compound in the presence of an acid catalyst. Phenolic compounds include, for example, o-, m- or p-cresol, 2,5-, 3,5- or 3,4-xylenol, 2,3,5-trimethylphenol, 2-t-butyl-5 -methylphenol and t-butylhydroquinone. Aldehyde compounds include, for example, aliphatic aldehydes (eg formaldehyde, acetaldehyde and glyoxal) and aromatic aldehydes (eg benzaldehyde and salicylaldehyde). Acid catalysts include, for example, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as oxalic acid, acetic acid and p-toluenesulfonic acid and divalent metal salts such as zinc acetate. . A condensation reaction can be performed according to a conventional method. The condensation reaction is carried out, for example, at a temperature in the range of 60° C. to 120° C. for 2 hours to 30 hours. The condensation reaction may be carried out in a suitable solvent.

Among them, as the alkali-soluble resin, a resin having a structural unit having a phenolic hydroxyl group, such as a novolak resin, is preferable.

The weight average molecular weight of the alkali-soluble resin is preferably 5.0×10 ² to 2.0×10 ⁵ from the viewpoint of pattern formability. The number average molecular weight of the alkali-soluble resin is preferably 2.0×10 ² to 1.0×10 ⁵ from the viewpoint of pattern formability.

For example, an alkyl group having 3 to 8 carbon atoms as a substituent, such as a condensation polymer of t-butylphenol and formaldehyde and a condensation polymer of octylphenol and formaldehyde described in US Pat. No. 4,123,279. A condensation polymer of phenol and formaldehyde may be used in combination. A condensate of phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as a substituent such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin described in US Pat. No. 4,123,279 is used in combination. may

The positive photosensitive resin layer may contain one type of single or two or more types of alkali-soluble resins.
The content of the alkali-soluble resin is preferably 30% by mass to 99.9% by mass, more preferably 40% by mass to 99.5% by mass, based on the total mass of the positive photosensitive resin layer. Preferably, it is particularly preferably 70% by mass to 99% by mass.

<<Photo acid generator>>
The positive photosensitive resin layer preferably contains a photoacid generator as a photosensitive compound. A photoacid generator is a compound that can generate an acid upon irradiation with actinic rays (eg, ultraviolet rays, deep ultraviolet rays, X-rays, and electron beams).

The photoacid generator is preferably a compound that generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm. Also, for photoacid generators that do not directly react to actinic rays with a wavelength of 300 nm or longer, if they are compounds that generate an acid by being sensitized to actinic rays with a wavelength of 300 nm or longer by being used in combination with a sensitizer, the sensitizer can be used. It can be preferably used in combination with.

The photoacid generator is preferably a photoacid generator that generates an acid with a pKa of 4 or less, more preferably a photoacid generator that generates an acid with a pKa of 3 or less, and more preferably a photoacid generator that generates an acid with a pKa of 2 or less. A photoacid generator that generates an acid is particularly preferred. The lower limit of the pKa of the acid derived from the photoacid generator is not restricted. The pKa of the acid derived from the photoacid generator is preferably -10.0 or more, for example.

Examples of photoacid generators include ionic photoacid generators and nonionic photoacid generators.

Examples of ionic photoacid generators include onium salt compounds. Onium salt compounds include, for example, diaryliodonium salt compounds, triarylsulfonium salt compounds, and quaternary ammonium salt compounds. The ionic photoacid generator is preferably an onium salt compound, particularly preferably at least one of a triarylsulfonium salt compound and a diaryliodonium salt compound.

As the ionic photoacid generator, the ionic photoacid generators described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.

Nonionic photoacid generators include, for example, trichloromethyl-s-triazine compounds, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds. The nonionic photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion to substrates.

Specific examples of the trichloromethyl-s-triazine compound, diazomethane compound, and imidosulfonate compound include compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494.

As the oxime sulfonate compound, those described in paragraphs 0084 to 0088 of WO 2018/179640 can be preferably used.

From the viewpoint of sensitivity and resolution, the photoacid generator is preferably at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, more preferably an oxime sulfonate compound.

Preferred examples of photoacid generators include photoacid generators having the following structures.

Examples of the photoacid generator having absorption at a wavelength of 405 nm include ADEKA Arkles (registered trademark) SP-601 (manufactured by ADEKA Corporation).

From the viewpoint of heat resistance and dimensional stability, the positive photosensitive resin layer preferably contains a quinonediazide compound as an acid generator (preferably a photoacid generator).
A quinonediazide compound can be synthesized, for example, by condensation reaction of a compound having a phenolic hydroxyl group and a quinonediazide sulfonic acid halide in the presence of a dehydrohalogenating agent.

Examples of quinonediazide compounds include 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,2- naphthoquinonediazide-6-sulfonate, 2,1-naphthoquinonediazide-4-sulfonate, 2,1-naphthoquinonediazide-5-sulfonate, 2,1-naphthoquinonediazide-6-sulfonate, and other Sulfonic acid esters of quinonediazide derivatives, 1,2-benzoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2- naphthoquinonediazide-6-sulfonyl chloride, 2,1-naphthoquinonediazide-4-sulfonyl chloride, 2,1-naphthoquinonediazide-5-sulfonyl chloride and 2,1-naphthoquinonediazide-6-sulfonyl chloride. .

The positive photosensitive resin layer may contain one kind of photoacid generator, or may contain two or more kinds of photoacid generators.
The content of the photoacid generator is preferably 0.1% by mass to 10% by mass, preferably 0.5% by mass, relative to the total mass of the positive photosensitive resin layer, from the viewpoint of sensitivity and resolution. It is more preferably ~5% by mass.

<<Other Ingredients>>
The photosensitive resin layer may contain components other than those mentioned above.

-Surfactant-
From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant.
Examples of surfactants include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, with nonionic surfactants being preferred.
Examples of surfactants include surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.

As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable.
Commercially available fluorosurfactants include, for example, Megafac (trade name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 , F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F -556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS -578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90 , R-94, RS-72-K, DS-21 (manufactured by DIC Corporation), Florard (trade names) FC430, FC431, FC171 (manufactured by Sumitomo 3M Ltd.), Surflon (trade name) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Co., Ltd.), PolyFox (Product names) PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), Futergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G , 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured by NEOS Corporation) and the like.
Fluorine-based surfactants also include acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes. It can be used preferably. As such a fluorosurfactant, Megafac (trade name) DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)) , for example, Megafac (trade name) DS-21.

It is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant.
A block polymer can also be used as the fluorosurfactant. The fluorosurfactant has 2 or more (preferably 5 or more) structural units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group and a propyleneoxy group) (meta). A fluorine-containing polymer compound containing structural units derived from an acrylate compound can also be preferably used.
A fluoropolymer having an ethylenically unsaturated group in a side chain can also be used as the fluorosurfactant. Megafac (trade name) RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation) and the like.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2 , 25R2 (manufactured by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse (trade name) 20000 (manufactured by Nippon Lubrizol Co., Ltd.) ), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Pionin (trade names) D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), OLFINE E1010, Surfynol 104, 400, 440 (manufactured by Nissin Kagaku Kogyo Co., Ltd.).
In recent years, compounds having a linear perfluoroalkyl group having 7 or more carbon atoms are concerned about their environmental suitability. It is preferred to use surfactants using materials.

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains or terminals.
Specific examples of silicone surfactants include DOWSIL (trade name) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400. (above, manufactured by Dow Corning Toray Co., Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440 , TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (manufactured by BYK-Chemie) and the like.

The photosensitive resin layer may contain one type of surfactant alone, or two or more types thereof.
The content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive resin layer.

-Additive-
The photosensitive resin layer may contain known additives, if necessary, in addition to the above components.
Additives include, for example, polymerization inhibitors, sensitizers, plasticizers, alkoxysilane compounds, and solvents. The photosensitive resin layer may contain each additive singly or in combination of two or more.
Additives include metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic suspending agents. Preferred aspects of these additives are described in paragraphs 0165 to 0184 of JP-A-2014-85643, the contents of which are incorporated herein by reference.

The photosensitive resin layer may contain a polymerization inhibitor. As the polymerization inhibitor, a radical polymerization inhibitor is preferred.
Examples of polymerization inhibitors include thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784 . Among them, phenothiazine, phenoxazine and 4-methoxyphenol are preferred. Other polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. In order not to impair the sensitivity of the photosensitive resin composition, it is preferred to use a nitrosophenylhydroxyamine aluminum salt as a polymerization inhibitor.

The content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, more preferably 0.05% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer. Setting the content to 0.01% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin composition. On the other hand, setting the content to 3% by mass or less is preferable from the viewpoint of maintaining sensitivity.

The photosensitive resin layer may contain a sensitizer.
The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used. Sensitizers include, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

The photosensitive resin layer may contain one type of sensitizer alone, or may contain two or more types.
When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing speed due to the balance between the polymerization speed and the chain transfer. Therefore, it is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 1% by mass, based on the total mass of the photosensitive resin layer.

The photosensitive resin layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds.
Plasticizers and heterocyclic compounds include compounds described in paragraphs 0097-0103 and 0111-0118 of WO2018/179640.

The photosensitive resin layer, preferably the positive photosensitive resin layer, may contain an alkoxysilane compound.
Examples of alkoxysilane compounds include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxysilane. propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane, and vinyltrialkoxysilane Silanes are mentioned.

Among the above, the alkoxysilane compound is preferably a trialkoxysilane compound, more preferably γ-glycidoxypropyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane, and γ-glycidoxy More preferred is propyltrialkoxysilane, and particularly preferred is 3-glycidoxypropyltrimethoxysilane.

The photosensitive resin layer may contain a single alkoxysilane compound, or may contain two or more alkoxysilane compounds.
The content of the alkoxysilane compound is preferably 0.1% by mass to 50% by mass, preferably 0.5% by mass, based on the total mass of the photosensitive resin layer, from the viewpoint of adhesion to the substrate and etching resistance. % to 40% by mass, and particularly preferably 1.0% to 30% by mass.

The photosensitive resin layer may contain a solvent. When the photosensitive resin layer is formed from a photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive resin layer.

<<impurities, etc.>>
The photosensitive resin layer may contain a predetermined amount of impurities.
Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens and ions thereof. Among them, halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the following contents are preferable.

The content of impurities in the photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less on a mass basis. The content of impurities can be 1 ppb or more, and may be 0.1 ppm or more, on a mass basis.

As a method for adjusting the impurity content to the above range, it is possible to select a raw material of the composition with a low content of impurities, to prevent contamination of impurities during the preparation of the photosensitive resin layer, and to remove impurities by washing. be done. By such a method, the amount of impurities can be made within the above range.

Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

The content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive resin layer should be small. is preferred. The content of these compounds with respect to the total mass of the photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, based on mass.
The lower limit can be 10 ppb or more, and can be 100 ppb or more based on the total weight of the photosensitive resin layer. The content of these compounds can be suppressed in the same manner as the metal impurities described above. Moreover, it can quantify by a well-known measuring method.

The water content in the photosensitive resin layer is preferably 0.01% by mass to 1.0% by mass, more preferably 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and lamination properties. .

<<Residual monomer>>
The photosensitive resin layer may contain residual monomers corresponding to the constituent units of the alkali-soluble resin described above.
The content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and 500 ppm by mass or less, relative to the total mass of the alkali-soluble resin, from the viewpoints of patterning properties and reliability. is more preferred. Although the lower limit is not particularly limited, it is preferably 1 mass ppm or more, more preferably 10 mass ppm or more.
The residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, relative to the total mass of the photosensitive resin layer, from the viewpoints of patterning properties and reliability. , 100 ppm by mass or less is more preferable. Although the lower limit is not particularly limited, it is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more.

It is preferable that the amount of residual monomers in synthesizing the alkali-soluble resin by polymer reaction is also within the above range. For example, when synthesizing an alkali-soluble resin by reacting a carboxylic acid side chain with glycidyl acrylate, the content of glycidyl acrylate is preferably within the above range.
The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

<<physical properties>>
The layer thickness of the photosensitive resin layer is preferably 0.1 μm to 300 μm, more preferably 0.2 μm to 100 μm, still more preferably 0.5 μm to 50 μm, even more preferably 0.5 μm to 15 μm, and 0.5 μm to 10 μm. is particularly preferred, and 0.5 μm to 8 μm is most preferred. Thereby, the developability of the photosensitive resin layer is improved, and the resolution can be improved.
In addition, the layer thickness (thickness) of the photosensitive resin layer is preferably 10 μm or less, more preferably 5.0 μm or less, from the viewpoint of exhibiting the resolution and the effects of the present disclosure. , more preferably 0.5 μm to 4.0 μm, particularly preferably 0.5 μm to 3.0 μm.
The layer thickness of each layer included in the photosensitive transfer material is based on an observation image obtained by observing a cross section in a direction perpendicular to the main surface of the photosensitive transfer material with a scanning electron microscope (SEM). It is measured by measuring the thickness of each layer at 10 points or more and calculating the average value.

Further, from the viewpoint of better adhesion, the transmittance of the photosensitive resin layer for light having a wavelength of 365 nm is preferably 10% or more, preferably 30% or more, and more preferably 50% or more. Although the upper limit is not particularly limited, 99.9% or less is preferable.

<<Method of Formation>>
The method for forming the photosensitive resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
As a method for forming a photosensitive resin layer, for example, in the case of a negative photosensitive resin layer, a photosensitive resin composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, a solvent, etc. is prepared, and a temporary A method of applying a photosensitive resin composition to the surface of a support or the like and drying the coated film of the photosensitive resin composition may be used.

The photosensitive resin composition used for forming the photosensitive resin layer includes, for example, a composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, any of the above optional components, and a solvent.
The photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer.

-solvent-
The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the alkali-soluble resin, the polymerizable compound, the photopolymerization initiator and the above optional components, and known solvents can be used.
Examples of solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents. (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of these.
When producing a photosensitive transfer material comprising a temporary support, a thermoplastic resin layer, a water-soluble resin layer, a photosensitive resin layer and a protective film, the photosensitive resin composition is selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. It is preferable to contain at least one selected from the group consisting of: Among them, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferable. A mixed solvent containing at least one selected from the group consisting of a glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent is more preferable.

Alkylene glycol ether solvents include, for example, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether. .
Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.
As the solvent, the solvent described in paragraphs 0092 to 0094 of WO 2018/179640, and the solvent described in paragraph 0014 of JP 2018-177889 may be used, the contents of which are herein incorporated into the book.

The photosensitive resin composition may contain one type of solvent alone, or may contain two or more types.
The content of the solvent when applying the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. part is more preferred.

The method for preparing the photosensitive resin composition is not particularly limited, for example, by preparing a solution in which each component is dissolved in the solvent in advance and mixing the resulting solution in a predetermined ratio, the photosensitive resin composition and a method for preparing the
From the viewpoint of removability of particles, the photosensitive resin composition is preferably filtered using a filter before forming the photosensitive resin layer, and it is preferable to filter using a filter having a pore size of 0.2 μm to 10 μm. More preferably, it is filtered using a filter with a pore size of 0.2 μm to 7 μm, and particularly preferably with a filter with a pore size of 0.2 μm to 5 μm.
The material and shape of the filter are not particularly limited, and known filters can be used.
Moreover, it is preferable to perform said filtration once or more, and it is also preferable to perform multiple times.

The method of applying the photosensitive resin composition is not particularly limited, and a known method may be used. Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating.
Also, the photosensitive resin layer may be formed by applying a photosensitive resin composition onto a protective film described below and drying the composition.

In addition, the photosensitive transfer material in the present disclosure preferably has another layer between the temporary support and the photosensitive resin layer from the viewpoint of resolution and peelability of the temporary support. .
Other layers preferably include a water-soluble resin layer, a thermoplastic resin layer, a protective film, and the like.
Among them, the transfer layer preferably has a water-soluble resin layer, and more preferably has a thermoplastic resin layer and a water-soluble resin layer.

[Water-soluble resin layer]
If the photosensitive transfer material has a thermoplastic resin layer described later between the temporary support and the photosensitive resin layer, it should have a water-soluble resin layer between the thermoplastic resin layer and the photosensitive resin layer. is preferred. According to the water-soluble resin layer, it is possible to suppress mixing of components when forming a plurality of layers and during storage.

The water-soluble resin layer is preferably a water-soluble layer from the viewpoint of developability and suppression of mixing of components during coating of multiple layers and storage after coating. In the present disclosure, "water-soluble" means that the solubility in 100 g of water at pH 7.0 at a liquid temperature of 22°C is 0.1 g or more.

Examples of the water-soluble resin layer include an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A-5-72724. Since the water-soluble resin layer is an oxygen-blocking layer, the sensitivity during exposure is improved and the time load of the exposure machine is reduced, resulting in improved productivity. The oxygen barrier layer used as the water-soluble resin layer may be appropriately selected from known layers. The oxygen-blocking layer used as the water-soluble resin layer is preferably an oxygen-blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22°C). .
In addition, the water-soluble resin layer preferably contains an inorganic stratiform compound from the viewpoints of oxygen blocking properties, resolution, and pattern formability.
Examples of the inorganic layered compound include particles having a thin tabular shape, and examples thereof include mica compounds such as natural mica and synthetic mica, talc represented by the formula: 3MgO.4SiO.H ₂ O, taeniolite, montmorillonite, saponite, hectorite, zirconium phosphate, and the like.
Examples of mica compounds include compounds of the formula: A(B,C) _2-5 D ₄ O ₁₀ (OH,F,O) ₂ [wherein A is any one of K, Na and Ca, and B and C are Fe(II), Fe(III), Mn, Al, Mg, or V, and D is Si or Al. ] and a group of mica such as natural mica and synthetic mica.

In the mica group, natural micas include muscovite, soda mica, phlogopite, biotite and lepidite. Synthetic mica includes _non -swelling mica such as fluorine phlogopite _KMg3 ( _AlSi3O10 ) _F2 , potash tetrasilicon mica _KMg2.5Si4O10 ) _F2 , and _Na tetrasilic _mica NaMg2 _{. 5} (Si ₄ O ₁₀ ) F ₂ , Na or Li teniolite (Na, Li) Mg ₂ Li(Si ₄ O ₁₀ ) F ₂ , montmorillonite Na or Li hectorite (Na, Li) _1/8 Mg _2/ Swellable mica such as ₅ Li _1/8 (Si ₄ O ₁₀ )F ₂ and the like are included. Also useful are synthetic smectites.

As for the shape of the inorganic layered compound, from the viewpoint of diffusion control, the thinner the thickness, the better. Therefore, the aspect ratio is preferably 20 or more, more preferably 100 or more, particularly preferably 200 or more. Aspect ratio is the ratio of the major axis to the thickness of the grain and can be determined, for example, from a micrograph projection of the grain. The larger the aspect ratio, the greater the effect that can be obtained.

As for the particle size of the inorganic layered compound, the average major axis is preferably 0.3 μm to 20 μm, more preferably 0.5 μm to 10 μm, and particularly preferably 1 μm to 5 μm. The average thickness of the particles is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.01 μm or less. Specifically, for example, in the case of swelling synthetic mica, which is a representative compound, a preferred embodiment has a thickness of about 1 nm to 50 nm and a plane size (major axis) of about 1 μm to 20 μm.

The content of the inorganic layered compound is preferably 0.1% by mass to 50% by mass, or 1% by mass, based on the total mass of the water-soluble resin layer, from the viewpoints of oxygen barrier properties, resolution, and pattern formability. % to 20% by mass is more preferred.

The water-soluble resin layer preferably contains a resin. Examples of resins contained in the water-soluble resin layer include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. coalescence is mentioned. The resin contained in the water-soluble resin layer is preferably a water-soluble resin.

From the viewpoint of suppressing mixing of components between a plurality of layers, the resin contained in the water-soluble resin layer is the polymer A contained in the negative photosensitive resin layer and the thermoplastic resin (alkali-soluble It is preferable that the resin is different from any of the resins).

In addition, the water-soluble resin layer preferably contains a water-soluble compound, and more preferably contains a water-soluble resin, from the viewpoints of oxygen barrier properties, developability, resolution, and pattern formability.
The water-soluble compound is not particularly limited, but from the viewpoint of oxygen blocking properties, developability, resolution, and pattern formation properties, water-soluble cellulose derivatives, polyhydric alcohols, and oxide adducts of polyhydric alcohols. , polyethers, phenol derivatives, and amide compounds, preferably at least one compound selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropylcellulose and hydroxypropylmethylcellulose More preferably, it is a kind of water-soluble resin.
Examples of water-soluble resins include resins such as water-soluble cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide resins, (meth)acrylate resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. mentioned.
Among them, the water-soluble compound preferably contains polyvinyl alcohol, more preferably polyvinyl alcohol, from the viewpoint of oxygen barrier properties, developability, resolution, and pattern formability.
The degree of hydrolysis of polyvinyl alcohol is not particularly limited, but is preferably 73 mol % to 99 mol % from the viewpoints of oxygen blocking properties, developability, resolution, and pattern formability.
Moreover, polyvinyl alcohol preferably contains ethylene as a monomer unit from the viewpoint of oxygen blocking properties, developability, resolution, and pattern formability.

The water-soluble resin layer preferably contains polyvinyl alcohol from the viewpoint of oxygen barrier properties and suppression of mixing of components during coating of multiple layers and storage after coating, and polyvinyl alcohol and polyvinylpyrrolidone. It is more preferable to include

The water-soluble resin layer may contain one resin alone or two or more resins.

The content of the water-soluble compound in the water-soluble resin layer should be within the total weight of the water-soluble resin layer from the viewpoint of oxygen barrier properties and suppression of mixing of components during coating of multiple layers and storage after coating. On the other hand, it is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, and 90% by mass to 100% by mass. % is particularly preferred.

Moreover, the water-soluble resin layer may contain an additive as needed. Additives include, for example, surfactants.

The thickness of the water-soluble resin layer is not restricted. The average thickness of the water-soluble resin layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. When the thickness of the water-soluble resin layer is within the above range, it is possible to suppress mixing of components during formation of a plurality of layers and during storage without lowering the oxygen barrier property, and during development. An increase in the removal time of the water-soluble resin layer can be suppressed.

The method for forming the water-soluble resin layer is not limited as long as it is a method capable of forming a layer containing the above components. As a method for forming the water-soluble resin layer, for example, a method of applying a water-soluble resin layer composition to the surface of a thermoplastic resin layer or a photosensitive resin layer and then drying the coating film of the water-soluble resin layer composition. is mentioned.

Examples of water-soluble resin layer compositions include compositions containing resins and optional additives. The water-soluble resin layer composition preferably contains a solvent in order to adjust the viscosity of the water-soluble resin layer composition and facilitate the formation of the water-soluble resin layer. The solvent is not limited as long as it can dissolve or disperse the resin. The solvent is preferably at least one selected from the group consisting of water and water-miscible organic solvents, more preferably water or a mixed solvent of water and a water-miscible organic solvent.

Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol or ethanol.

[Thermoplastic resin layer]
The photosensitive transfer material used in the present disclosure may have a thermoplastic resin layer. The photosensitive transfer material preferably has a thermoplastic resin layer between the temporary support and the photosensitive resin layer. Since the photosensitive transfer material has a thermoplastic resin layer between the temporary support and the photosensitive resin layer, the followability to the adherend is improved, and air bubbles between the adherend and the photosensitive transfer material are eliminated. This is because the adhesion between the layers is improved as a result of the suppression of contamination.

The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.

Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, Polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.

The alkali-soluble resin is preferably an acrylic resin from the viewpoint of developability and adhesion to the layer adjacent to the thermoplastic resin layer. Here, the "acrylic resin" is selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides. means a resin having at least one

In the acrylic resin, the ratio of the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid ester, and structural units derived from (meth)acrylic acid amide is It is preferably 50% by mass or more with respect to the total mass. In the acrylic resin, the ratio of the total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylic acid ester is 30% to 100% by mass with respect to the total mass of the acrylic resin. %, more preferably 50% by mass to 100% by mass.

Also, the alkali-soluble resin is preferably a polymer having an acid group. The acid group includes, for example, a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, with the carboxy group being preferred.

From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH/g or more, and more preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more. The upper limit of the acid value is not restricted. The acid value of the alkali-soluble resin is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less.

The carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited, and can be appropriately selected from known resins and used. The carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more includes, for example, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more among the polymers described in paragraph 0025 of JP-A-2011-95716, Among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more, and paragraphs 0053 to 0068 of JP-A-2016-224162. Among the binder polymers of (1), a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more can be mentioned.

The content of structural units having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, based on the total mass of the carboxyl group-containing acrylic resin. 12% by mass to 30% by mass is particularly preferable.

The alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth)acrylic acid, from the viewpoint of developability and adhesion to the layer adjacent to the thermoplastic resin layer.

Alkali-soluble resin may have a reactive group. The reactive group may be, for example, a group capable of addition polymerization. Reactive groups include, for example, ethylenically unsaturated groups, polycondensable groups (e.g., hydroxy groups, and carboxy groups), and polyaddition-reactive groups (e.g., epoxy groups and (blocked) isocyanate groups). be done.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and particularly preferably 20,000 to 50,000.

The thermoplastic resin layer may contain one type alone or two or more types of alkali-soluble resins.

The content of the alkali-soluble resin is preferably 10% by mass to 99% by mass with respect to the total mass of the thermoplastic resin layer, from the viewpoint of developability and adhesion to layers adjacent to the thermoplastic resin layer. It is preferably from 20% by mass to 90% by mass, still more preferably from 40% by mass to 80% by mass, and particularly preferably from 50% by mass to 70% by mass.

The thermoplastic resin layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm during color development, and a dye whose maximum absorption wavelength changes due to acid, base, or radical (hereinafter referred to as "dye B" ) is preferably included. Preferred embodiments of the dye B are the same as the preferred embodiments of the dye N described above, except for the points described later.

Dye B is preferably a dye whose maximum absorption wavelength changes with acid or radicals from the viewpoint of visibility in exposed areas, visibility in unexposed areas, and resolution, and the maximum absorption wavelength changes with acids. It is more preferable that it is a dye that

From the viewpoints of visibility in exposed areas, visibility in unexposed areas, and resolution, the thermoplastic resin layer contains a dye whose maximum absorption wavelength changes with an acid as dye B, and a compound C described later. is preferred.

The thermoplastic resin layer may contain one type of dye B alone or two or more types.

From the viewpoint of the visibility of the exposed area and the visibility of the non-exposed area, the content of the dye B is preferably 0.2% by mass or more with respect to the total mass of the thermoplastic resin layer, and is preferably 0.2% by mass. % to 6% by mass, more preferably 0.2% to 5% by mass, and particularly preferably 0.25% to 3.0% by mass.

Here, the content ratio of the dye B means the content ratio of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state. A method for quantifying the content of the dye B will be described below using a dye that develops color by radicals as an example. Prepare two solutions of dye (0.001 g) and dye (0.01 g) in methyl ethyl ketone (100 mL). After adding IRGACURE OXE01 (manufactured by BASF) as a photoradical polymerization initiator to each solution obtained, radicals are generated by irradiation with light of 365 nm, and all dyes are brought into a colored state. Next, in an air atmosphere, using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), the absorbance of each solution having a liquid temperature of 25° C. is measured to prepare a calibration curve. Next, the absorbance of the solution in which all the dyes are developed is measured in the same manner as described above except that the thermoplastic resin layer (0.1 g) is dissolved in methyl ethyl ketone instead of the dyes. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of dye contained in the thermoplastic resin layer is calculated based on the calibration curve.

The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical upon exposure to light (hereinafter sometimes referred to as "compound C"). Compound C is preferably a compound that receives actinic rays (eg, ultraviolet rays and visible rays) and generates an acid, a base, or a radical. Examples of the compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators). Compound C is preferably a photoacid generator.

From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. Examples of the photoacid generator include a photocationic polymerization initiator that may be contained in the photosensitive resin layer described above.

From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one selected from the group consisting of onium salt compounds and oxime sulfonate compounds. From a viewpoint, it is more preferable to contain an oxime sulfonate compound.

Also, the photoacid generator is preferably a photoacid generator having the following structure.

The thermoplastic resin layer may contain a photobase generator. Examples of photobase generators include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[ [(2-Nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylamino Propane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt (III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2,6 -dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1, 4-dihydropyridine may be mentioned.

The thermoplastic resin layer may contain a radical photopolymerization initiator. The radical photopolymerization initiator includes, for example, the radical photopolymerization initiator that may be contained in the photosensitive resin layer described above, and preferred embodiments are also the same.

The thermoplastic resin layer may contain compound C singly or in combination of two or more.

The content of compound C is 0.1% by mass to 10% by mass with respect to the total mass of the thermoplastic resin layer, from the viewpoints of visibility of exposed areas, visibility of unexposed areas, and resolution. is preferred, and 0.5% by mass to 5% by mass is more preferred.

The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to layers adjacent to the thermoplastic resin layer, and developability.

The molecular weight of the plasticizer (weight average molecular weight (Mw) for the molecular weight of the oligomer or polymer; hereinafter the same applies in this paragraph) is preferably smaller than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200-2,000.

The plasticizer is not limited as long as it is a compound compatible with the alkali-soluble resin and exhibiting plasticity. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound having an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

The plasticizer preferably contains a (meth)acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution, and adhesion to the layer adjacent to the thermoplastic resin layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

The (meth)acrylate compound used as the plasticizer includes, for example, the (meth)acrylate compounds described in the ethylenically unsaturated compound. In the photosensitive transfer material, when the thermoplastic resin layer and the photosensitive resin layer are arranged in direct contact, the thermoplastic resin layer and the photosensitive resin layer may each contain the same (meth)acrylate compound. preferable. This is because the thermoplastic resin layer and the photosensitive resin layer each contain the same (meth)acrylate compound, thereby suppressing the diffusion of components between layers and improving the storage stability.

When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, the (meth)acrylate compound may not be polymerized even in the exposed areas after exposure from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer. preferable.

In one embodiment, the (meth)acrylate compound used as a plasticizer has two or more ( A (meth)acrylate compound having a meth)acryloyl group is preferred.

In one embodiment, the (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound.

The thermoplastic resin layer may contain a single plasticizer or two or more plasticizers.

The content of the plasticizer is 1% by mass to 70% by mass with respect to the total mass of the thermoplastic resin layer, from the viewpoints of resolution, adhesion with a layer adjacent to the thermoplastic resin layer, and developability. preferably 10% by mass to 60% by mass, particularly preferably 20% by mass to 50% by mass.

From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. Examples of surfactants include surfactants that may be contained in the photosensitive resin layer described above, and preferred embodiments are also the same.

The thermoplastic resin layer may contain a single surfactant or two or more surfactants.

The content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the thermoplastic resin layer.

The thermoplastic resin layer may contain a sensitizer. Examples of sensitizers include sensitizers that may be contained in the negative photosensitive resin layer described above.

The thermoplastic resin layer may contain one type of sensitizer or two or more types of sensitizers.

The content of the sensitizer is 0.01% by mass to 5% by mass with respect to the total mass of the thermoplastic resin layer, from the viewpoint of improving the sensitivity to the light source, the visibility of the exposed area, and the visibility of the non-exposed area. %, more preferably 0.05% by mass to 1% by mass.

The thermoplastic resin layer may contain known additives, if necessary, in addition to the above components.

Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A-2014-85643. The contents of the above publication are incorporated herein by reference.

The thickness of the thermoplastic resin layer is not restricted. The average thickness of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer. The upper limit of the average thickness of the thermoplastic resin layer is not restricted. The average thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less, from the viewpoint of developability and resolution.

The method for forming the thermoplastic resin layer is not limited as long as it is a method capable of forming a layer containing the above components. Examples of the method for forming the thermoplastic resin layer include a method of applying a thermoplastic resin composition to the surface of the temporary support and drying the coating film of the thermoplastic resin composition.

Examples of thermoplastic resin compositions include compositions containing the above components. The thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.

The solvent contained in the thermoplastic resin composition is not limited as long as it can dissolve or disperse the components contained in the thermoplastic resin layer. Examples of the solvent include solvents that may be contained in the photosensitive resin composition described above, and preferred embodiments are also the same.

The thermoplastic resin composition may contain one solvent alone or two or more solvents.

The content of the solvent in the thermoplastic resin composition is preferably 50 parts by mass to 1,900 parts by mass with respect to 100 parts by mass of the total solid content in the thermoplastic resin composition, and 100 parts by mass to 900 parts by mass. Part is more preferred.

Preparation of the thermoplastic resin composition and formation of the thermoplastic resin layer may be carried out according to the method of preparing the photosensitive resin composition and the method of forming the negative photosensitive resin layer described above. For example, a solution in which each component contained in the thermoplastic resin layer is dissolved in a solvent is prepared in advance, and the obtained solutions are mixed in a predetermined ratio to prepare a thermoplastic resin composition. A thermoplastic resin layer can be formed by applying a thermoplastic resin composition to the surface of a temporary support and drying the coating film of the thermoplastic resin composition. Moreover, after forming a photosensitive resin layer on the protective film, a thermoplastic resin layer may be formed on the surface of the photosensitive resin layer.

〔Protective film〕
The photosensitive transfer material preferably has a protective film.
Note that the protective film is not included in the transfer layer.
It is preferable that the photosensitive resin layer and the protective film are in direct contact with each other.

Materials constituting the protective film include resin films and paper, and resin films are preferable from the viewpoint of strength and flexibility.
Resin films include polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among them, polyethylene film, polypropylene film, or polyethylene terephthalate film is preferable.

The thickness (layer thickness) of the protective film is not particularly limited, but is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm.
The arithmetic mean roughness Ra of the surface of the protective film opposite to the photosensitive resin layer side is the photosensitive resin layer in the protective film from the viewpoint of transportability, defect suppression of the resin pattern, and resolution. It is preferably less than or equal to the arithmetic mean roughness Ra of the side surface, and more preferably less than the arithmetic mean roughness Ra of the photosensitive resin layer side surface of the protective film.
The arithmetic mean roughness Ra of the surface of the protective film opposite to the photosensitive resin layer side is preferably 300 nm or less, more preferably 100 nm or less, and even more preferably 70 nm or less, from the viewpoint of transportability and winding properties. 50 nm or less is particularly preferred.
In addition, the arithmetic mean roughness Ra of the surface of the protective film on the photosensitive resin layer side is preferably 300 nm or less, more preferably 100 nm or less, even more preferably 70 nm or less, and 50 nm or less from the viewpoint of better resolution. is particularly preferred. It is considered that the thickness uniformity of the photosensitive resin layer and the formed resin pattern is improved when the Ra value of the surface of the protective film is within the above range.
Although the lower limit of the Ra value on the surface of the protective film is not particularly limited, it is preferably 1 nm or more, more preferably 10 nm or more, and particularly preferably 20 nm or more for both surfaces.
Moreover, the peeling force of the protective film is preferably smaller than the peeling force of the temporary support.

The photosensitive transfer material may include layers other than the layers described above (hereinafter also referred to as "other layers"). Other layers include, for example, a contrast enhancement layer.
Contrast enhancement layers are described in paragraph 0134 of WO2018/179640. Other layers are described in paragraphs 0194 to 0196 of JP-A-2014-85643. The contents of these publications are incorporated herein.

The total thickness of the photosensitive transfer material is preferably 5 μm to 55 μm, more preferably 10 μm to 50 μm, particularly preferably 20 μm to 40 μm. The total thickness of the photosensitive transfer material is measured according to the method for measuring the thickness of each layer described above.
The total thickness of each layer in the photosensitive transfer material excluding the temporary support and the protective film is preferably 20 μm or less, more preferably 10 μm or less, and 8 μm or less from the viewpoint of exhibiting the effects of the present disclosure. It is more preferable to be 2 μm or more, and particularly preferably 2 μm or more and 8 μm or less.
Further, the total thickness of the photosensitive resin layer, the water-soluble resin layer and the thermoplastic resin layer in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, from the viewpoint of exhibiting the effects of the present disclosure. is more preferable, 8 μm or less is still more preferable, and 2 μm or more and 8 μm or less is particularly preferable.

[Method for producing photosensitive transfer material]
The method for producing the photosensitive transfer material used in the present disclosure is not particularly limited, and known production methods such as known methods for forming each layer can be used.
A method for manufacturing a photosensitive transfer material used in the present disclosure will be described below with reference to FIG. However, the photosensitive transfer material used in the present disclosure is not limited to those having the configuration shown in FIG.
FIG. 1 is a schematic cross-sectional view showing an example of a layer structure in one embodiment of a photosensitive transfer material used in the present disclosure. The photosensitive transfer material 20 shown in FIG. 1 has a structure in which a temporary support 11, a thermoplastic resin layer 13, a water-soluble resin layer 15, a photosensitive resin layer 17, and a protective film 19 are laminated in this order. have. The transfer layer 12 in FIG. 1 includes the thermoplastic resin layer 13, the water-soluble resin layer 15, and the photosensitive resin layer 17. FIG.

As a method for producing the photosensitive transfer material 20, for example, after applying a thermoplastic resin composition to the surface of the temporary support 11, by drying the coating film of the thermoplastic resin composition, the thermoplastic resin layer a step of forming a water-soluble resin layer 15 by applying a water-soluble resin layer composition to the surface of the thermoplastic resin layer 13 and then drying the coating film of the water-soluble resin layer composition; a step of applying a photosensitive resin composition containing an ethylenically unsaturated compound to the surface of the water-soluble resin layer 15 and then drying the coating film of the photosensitive resin composition to form the photosensitive resin layer 16. method.
In the above production method, a thermoplastic resin composition containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, and selected from the group consisting of water and water-miscible organic solvents and a binder polymer, an ethylenically unsaturated compound, and at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. It is preferable to use a flexible resin composition. As a result, the water-soluble resin layer composition is applied to the surface of the thermoplastic resin layer 13 and / or contained in the thermoplastic resin layer 13 during the storage period of the laminate having the coating film of the water-soluble resin layer composition. It is possible to suppress mixing of the component contained in the water-soluble resin layer 15 with the component contained in the water-soluble resin layer 15, and the application of the photosensitive resin composition to the surface of the water-soluble resin layer 15 and / or the photosensitive resin composition mixing of the components contained in the water-soluble resin layer 15 and the components contained in the photosensitive resin layer 16 during the storage period of the laminate having the coating film can be suppressed.

The photosensitive transfer material 20 is manufactured by pressing the protective film 19 onto the photosensitive resin layer 17 of the laminate manufactured by the manufacturing method described above.
As a method for producing the photosensitive transfer material used in the present disclosure, by including a step of providing a protective film 19 so as to be in contact with the second surface of the photosensitive resin layer 17, the temporary support 11, the thermoplastic resin layer 13, It is preferable to manufacture a photosensitive transfer material 20 comprising a water-soluble resin layer 15 , a photosensitive resin layer 17 and a protective film 19 .
After manufacturing the photosensitive transfer material 20 by the manufacturing method described above, the photosensitive transfer material 20 may be wound up to produce and store a roll-shaped photosensitive transfer material. The photosensitive transfer material in roll form can be provided as it is to the lamination step with a substrate in a roll-to-roll system, which will be described later.

<Pigment>
The photosensitive resin layer may be a colored resin layer containing a pigment.
In order to protect the liquid crystal display window of electronic equipment in recent years, there are cases where a cover glass with a black frame-shaped light shielding layer formed on the periphery of the back surface of a transparent glass substrate or the like is attached in order to protect the liquid crystal display window. be. A colored resin layer may be used to form such a light shielding layer.
The pigment may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and chromatic pigments other than black and white. Among them, when forming a black pattern, a black pigment is preferably selected as the pigment.

As the black pigment, a known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as it does not impair the effects of the present disclosure. Among them, from the viewpoint of optical density, black pigments include, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide and graphite, and carbon black is particularly preferred. As the carbon black, from the viewpoint of surface resistance, carbon black having at least a part of the surface coated with a resin is preferable.

From the viewpoint of dispersion stability, the number average particle size of the black pigment is preferably 0.001 μm to 0.1 μm, more preferably 0.01 μm to 0.08 μm.
Here, the particle size refers to the diameter of a circle obtained by obtaining the area of a pigment particle from a photographic image of the pigment particle taken with an electron microscope and considering a circle having the same area as the area of the pigment particle. is an average value obtained by obtaining the above particle size for 100 arbitrary particles and averaging the obtained 100 particle sizes.

White pigments described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used as pigments other than black pigments. Specifically, among white pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferable as inorganic pigments, and titanium oxide or zinc oxide is more preferable. Preferred, and more preferred is titanium oxide. As the inorganic pigment, rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable.
In addition, the surface of titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic substance treatment, or may be subjected to two or more treatments. As a result, the catalytic activity of titanium oxide is suppressed, and the heat resistance, fade resistance, and the like are improved.
From the viewpoint of reducing the thickness of the photosensitive resin layer after heating, the surface treatment of the titanium oxide surface is preferably at least one of alumina treatment and zirconia treatment, and particularly preferably both alumina treatment and zirconia treatment.

Moreover, when the photosensitive resin layer is a colored resin layer, from the viewpoint of transferability, the photosensitive resin layer preferably further contains a chromatic pigment other than the black pigment and the white pigment. When a chromatic pigment is included, the particle size of the chromatic pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of better dispersibility.
Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter C.I.) 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), and Monolite.・Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C) Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B Spra (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. Pigment Black 1) and Carbon, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64, and C.I. I. Pigment Violet 23 and the like. Among them, C.I. I. Pigment Red 177 is preferred.

When the photosensitive resin layer contains a pigment, the content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, relative to the total mass of the photosensitive resin layer. , more preferably more than 5% by mass and 35% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less.

When the photosensitive resin layer contains pigments other than black pigments (white pigments and chromatic pigments), the content of pigments other than black pigments is preferably 30% by mass or less, and 1% by mass to 20% by mass is more preferable, and 3% to 15% by mass is even more preferable.

In addition, when the photosensitive resin layer contains a black pigment and the photosensitive resin layer is formed of a photosensitive resin composition, the black pigment (preferably carbon black) is added to the photosensitive resin composition in the form of a pigment dispersion. It is preferably introduced into an object.
The dispersion liquid may be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing the mixture with a dispersing machine. A pigment dispersant may be selected according to the pigment and solvent, and for example, a commercially available dispersant can be used. In addition, the vehicle refers to the part of the medium in which the pigment is dispersed in the case of a pigment dispersion, and is a liquid binder component that holds the black pigment in a dispersed state, and a solvent component that dissolves and dilutes the binder component. (Organic solvent) and.

The disperser is not particularly limited, and examples thereof include known dispersers such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Furthermore, it may be finely pulverized using frictional force by mechanical grinding. Regarding the dispersing machine and the fine pulverization, reference can be made to the description in "Encyclopedia of Pigment" (Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).

(Method for manufacturing electronic device)
The method for manufacturing an electronic device according to the present disclosure is not particularly limited as long as it is a method for manufacturing an electronic device including a substrate having a conductive pattern obtained by the method for manufacturing a substrate having a conductive pattern according to the present disclosure.

Specific aspects of each step in the method for manufacturing an electronic device, and embodiments such as the order of performing each step are as described in the above section "Method for manufacturing a conductive pattern", and preferred aspects are also It is the same.
As for the method for manufacturing an electronic device, a known method for manufacturing an electronic device may be referred to, except that the electronic device wiring is formed by the method described above.
Moreover, the method for manufacturing an electronic device may include arbitrary steps (other steps) other than those described above.

Electronic devices are not particularly limited, but semiconductor packages, printed circuit boards, various wiring formation applications for sensor substrates, touch panels, electromagnetic wave shielding materials, conductive films such as film heaters, liquid crystal sealing materials, micromachines or in the field of microelectronics Structures are preferred.
In the electronic device, the resin pattern is preferably used as a permanent film, such as an interlayer insulating film, a wiring protective film, or a wiring protective film having an index matching layer.
Among them, a touch panel is particularly suitable as an electronic device.
Moreover, as an electronic device, a flexible display device, particularly a flexible touch panel can be preferably mentioned.

An example of a mask pattern used for manufacturing a touch panel is shown in FIGS. 2 and 3. FIG.
In pattern A shown in FIG. 2 and pattern B shown in FIG. It is shown In the touch panel manufacturing method, for example, by exposing the photosensitive resin layer through a mask having a pattern A shown in FIG. . Specifically, it can be produced by the method described in FIG. 1 of International Publication No. 2016/190405. In one example of the manufactured touch panel, the central portion of the exposed portion EX (the pattern portion where the qualifications are connected) is the portion where the transparent electrode (touch panel electrode) is formed, and the peripheral portion (thin line portion) of the exposed portion EX is This is the portion where the wiring of the peripheral extracting portion is formed.

By the method for manufacturing an electronic device described above, an electronic device having at least electronic device wiring is manufactured, and preferably, a touch panel having at least touch panel wiring is manufactured, for example.
The touch panel preferably has a transparent substrate, electrodes, and an insulating layer or protective layer.
Known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method can be used as a detection method for a touch panel. Among them, the capacitance method is preferable.

As the touch panel type, the so-called in-cell type (for example, those described in FIGS. 5, 6, 7 and 8 of JP-A-2012-517051), the so-called on-cell type (for example, JP-A-2013-168125) Those described in FIG. 19 and those described in FIGS. 1 and 5 of JP-A-2012-89102), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP-A 2013-54727), various out-cell types (so-called GG, G1 G2, GFF, GF2, GF1 and G1F, etc.) and other configurations (for example, JP 2013-164871 6).
Examples of touch panels include those described in paragraph 0229 of JP-A-2017-120435.

(Substrate with conductive pattern)
A substrate having a conductive pattern according to the present disclosure includes a substrate, a first section in which a conductive pattern d containing a metal nanobody and a resin 1 is formed on at least one surface of the substrate, and the conductive pattern d. and a second section that is not formed, and the area where the void is observed when the second section is observed with a scanning electron microscope from the thickness direction of the substrate is the entirety of the second section It is 10% or less with respect to the area.
In the second compartment, the metal nanobodies have been removed, eg, by an etching process, and are substantially free of metal nanobodies. The state of being substantially free is a state in which the metal nano-body in the second compartment is removed and the inside of the compartment becomes an insulator. The presence of the first section and the second section enables formation of a conductive pattern circuit by the metal nano-body.
Moreover, in the second section, it is preferable that the resin in which the metal nano-body is dispersed remains without being removed. That is, it is preferable that the resin is present in the second section. In this case, the portion where the resin film that has not been removed by etching exists and is not a conductive pattern is the second section.
It should be noted that the second section may contain a substance other than the resin 1 as long as the insulation is not impaired. Substances other than resin 1 include other resins, polymerizable compounds, antioxidants, ultraviolet absorbers, polymerization initiators, antirust agents, and the like.
A substrate having a conductive pattern according to the present disclosure is preferably manufactured by a method for manufacturing a substrate having a conductive pattern according to the present disclosure.

The substrate, metal nanobody, resin 1, and conductive pattern d are the same as the substrate, metal nanobody, resin 1, and conductive pattern d described in the method for producing a substrate having a conductive pattern according to the present disclosure, and are preferred embodiments. are also the same.
In addition, other aspects are the same as the preferred embodiments described in the method for manufacturing a substrate having a conductive pattern according to the present disclosure.

The first section in the substrate having the conductive pattern according to the present disclosure is the portion where the conductive pattern d formed on the substrate exists, and the second section is the portion where the conductive pattern d does not exist.
In the substrate having a conductive pattern according to the present disclosure, the area where voids are observed when the second section is observed with a scanning electron microscope from the thickness direction of the substrate is the entire area of the second section. On the other hand, it is 10% or less, and from the viewpoint of the dimensional stability of the conductive pattern after energization, it is preferably 8% or less, more preferably 5% or less, and 0% or more and 3% or less. Especially preferred.

In the substrate having a conductive pattern according to the present disclosure, from the viewpoint of dimensional stability of the conductive pattern after energization, the layer thickness from the substrate surface of the first section is H1, and the substrate surface of the second section is It is preferable to satisfy 0.90≦H1/H2≦1.11, more preferably 0.95≦H1/H2≦1.05, where H2 is the layer thickness of the empty layer.
In addition, the number of recesses having a depth of 10 nm or more in the second section is preferably 10/100 μm ² or less, and 8/100 μm ² from the viewpoint of dimensional stability of the conductive pattern after energization. It is preferably 5/100 μm 2 or less, more preferably 5/100 μm ² or less, and particularly preferably 3/100 μm ² or less. The lower limit is 0/100 μm ² .

(Protective film for metal nano-body)
The metal nanobody protective film according to the present disclosure has a resin layer containing a resin having a glass transition temperature of 150° C. or less.
A preferable aspect of the resin layer in the protective film for metal nano-body according to the present disclosure is the same as the preferable aspect of the resin layer b described above.
In addition, a preferred embodiment of the resin having a glass transition temperature of 150° C. or lower in the protective film for metal nano-body according to the present disclosure is the same as the preferred embodiment of Resin 2 described above, except for the glass transition temperature.
The glass transition temperature of the resin having a glass transition temperature of 150° C. or less is preferably 30° C. to 140° C., more preferably 40° C. to 130° C., from the viewpoint of the dimensional stability of the conductive pattern after energization. 40° C. to 120° C. is particularly preferred.

The average thickness of the resin layer in the metal nanobody protective film according to the present disclosure is not particularly limited, but from the viewpoint of the dimensional stability of the conductive pattern after energization, it is preferably 1 nm to 200 nm, and 5 nm to 100 nm. more preferably 15 nm to 50 nm.

Moreover, the protective film for a metal nanobody according to the present disclosure preferably includes not only a mode in which the metal nanobody is directly contacted to protect it, but also a mode in which it is brought into contact with a layer containing the metal nanobody to protect it.

EXAMPLES The embodiments of the present invention will be described more specifically with reference to examples below. Materials, usage amounts, proportions, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the gist of the embodiments of the present invention. Accordingly, the scope of embodiments of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

(Examples 1 to 14 and Comparative Example 1)
<Preparation of conductive substrate>
A film (ClearOhm, manufactured by Cambrios) in which a conductive layer in which metal nanowires are dispersed in a resin (transmittance for light with a wavelength of 380 nm to 780 nm: 92%) is laminated on a substrate made of a polyethylene terephthalate film was prepared.
On this film, a composition for forming a protective layer having the composition shown in Table 1 was applied so as to give a film thickness of 40 nm after drying. After drying in an oven at 100° C., exposure was performed at an exposure dose of 600 mJ/cm ² using an exposure machine (M-1S, manufactured by Mikasa Co., Ltd.). Further, post-baking was performed in a convection oven at 140° C. for 30 minutes to form a protective layer (resin layer b).

In Examples 10, 13, and 14, since the composition of the protective layer did not contain a polymerizable compound, exposure was not performed after forming the protective layer.

The unit of the numerical value of each component shown in Table 1 is parts by mass.
Details of the abbreviations in Table 1 are as follows.
A-1: benzyl methacrylate/methacrylic acid = 70/30% by weight copolymer (molecular weight 30,000, propylene glycol monomethyl ether acetate 30% by weight solution), glass transition temperature 75°C
A-2: benzyl methacrylate/methacrylic acid/2-hydroxyethyl acrylate = 40/30/30% by weight copolymer (molecular weight 30,000, propylene glycol monomethyl ether acetate 30% by weight solution), glass transition temperature 41°C
A-3: Elitel UE-9990 (polyester resin, manufactured by Unitika Ltd.), glass transition temperature 101 ° C.
A-4: Elitel UE-3690 (polyester resin, manufactured by Unitika Ltd.), glass transition temperature 90 ° C.
A-5: Elitel UE-3980 (polyester resin, manufactured by Unitika Ltd.), glass transition temperature 63 ° C.
A-6: Dianal MB-2952 (acrylic resin, manufactured by Mitsubishi Chemical Corporation), glass transition temperature 85 ° C.
A-7: Dianal BR-113 (acrylic resin, manufactured by Mitsubishi Chemical Corporation), glass transition temperature 75 ° C.
A-8: S-lec KS-10 (polyvinyl acetal resin, manufactured by Sekisui Chemical Co., Ltd.), glass transition temperature 105 ° C.
A-9: S-lec BL-10 (polyvinyl butyral resin, manufactured by Sekisui Chemical Co., Ltd.), glass transition temperature 67 ° C.
A-10: Phenolite WR-104 (phenol novolac resin, manufactured by DIC Corporation), glass transition temperature 79 ° C.
A-11: CAP-504-0.2 (cellulose acetate propionate, Tomoe Kogyo Co., Ltd.), glass transition temperature 159 ° C.
B-1: Light acrylate DPE-6A (dipentaerythritol hexaacrylate, manufactured by Kyoeisha Chemical Co., Ltd.)
C-1: Irgacure OXE02 (photopolymerization initiator, manufactured by BASF Japan Ltd.)
D-1: BT-120 (1,2,3-benzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.)
F-1: propylene glycol monomethyl ether acetate F-2: methyl ethyl ketone

<Preparation of photosensitive transfer material>
On a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%), a coating width of 1.0 m and a dry layer thickness of 3 are applied to the surface of the temporary support using a slit nozzle. The following thermoplastic resin composition was applied so as to have a thickness of 0 μm. The formed coating film of the thermoplastic resin composition was dried at 80° C. for 40 seconds to form a thermoplastic resin layer.
The following water-soluble resin layer composition was applied to the surface of the formed thermoplastic resin layer using a slit nozzle so that the coating width was 1.0 m and the layer thickness after drying was 1.2 μm. The coating film of the water-soluble resin layer composition was dried at 80° C. for 40 seconds to form a water-soluble resin layer.
On the surface of the formed water-soluble resin layer, the following photosensitive resin composition is applied using a slit-shaped nozzle so that the coating width is 1.0 m and the layer thickness after drying is 5.0 μm, A photosensitive resin layer was formed by drying at 100° C. for 2 minutes. A protective film (polypropylene film, thickness: 12 μm) was laminated on the photosensitive resin layer to prepare a photosensitive transfer material.

<Composition of thermoplastic resin composition>
· Benzyl methacrylate, methacrylic acid and acrylic acid copolymer propylene glycol monomethyl ether acetate solution (solid concentration 30.0%, Mw 30,000, acid value 153 mgKOH / g): 42.85 parts · NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.): 4.33 parts 8UX-015A (manufactured by Taisei Fine Chemicals Co., Ltd.): 2.31 parts Aronix TO-2349 (manufactured by Toagosei Co., Ltd.): 0.77 parts Megafac F-552 (manufactured by DIC Corporation): 0.03 parts Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.): 39.80 parts Propylene glycol monomethyl ether acetate (manufactured by Showa Denko Co., Ltd.): 9.51 parts Below Compound having the structure shown (photoacid generator, compound synthesized according to the method described in paragraph 0227 of JP-A-2013-47765.): 0.32 parts

- A compound having the structure shown below (a dye that develops color with an acid): 0.08 parts

<Composition of water-soluble resin layer composition>
Kuraray Poval PVA-205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts by mass Polyvinylpyrrolidone K-30 (manufactured by Nippon Shokubai Co., Ltd.): 1.49 parts by mass Megafac F-444 (fluorosurfactant, DIC Corporation): 0.0015 parts by mass Ion-exchanged water: 38.12 parts by mass Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 57.17 parts by mass

<Composition of photosensitive resin composition>
Propylene glycol monomethyl ether acetate solution of copolymer of styrene/methacrylic acid/methyl methacrylate (solid content concentration: 30.0 mass%, ratio of each monomer: 52 mass%/29 mass%/19 mass%, Mw: 70 , 000): 23.4 parts by mass BPE-500 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin Nakamura Chemical Co., Ltd.): 4.1 parts by mass NK Ester HD-N (1,6-hexanediol dimethacrylate, new Nakamura Chemical Co., Ltd.): 2.2 parts by mass B-CIM (2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, Photopolymerization initiator, manufactured by Kurogane Kasei Co., Ltd.): 0.25 parts by mass SB-PI 701 (4,4'-bis (diethylamino) benzophenone, sensitizer, obtained from Sanyo Boeki Co., Ltd.): 0.04 mass Part TDP-G (phenothiazine, manufactured by Kawaguchi Chemical Industry Co., Ltd.): 0.0175 parts by mass 1-phenyl-3-pyrazolidone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 0.0011 parts by mass Leuco Crystal Violet (Tokyo Chemical Industry Co., Ltd.): 0.051 parts by mass N-phenylcarbamoylmethyl-N-carboxymethylaniline (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.): 0.02 parts by mass 1,2,4-triazole (Tokyo Chemical Industry Co., Ltd. manufactured by): 0.75 parts by mass Megafac F-552 (fluorosurfactant, manufactured by DIC Corporation): 0.05 parts by mass Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.): 40.4 parts by mass Propylene glycol monomethyl ether Acetate (manufactured by Showa Denko K.K.): 26.7 parts by mass Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.): 2 parts by mass

<Formation of Wiring Pattern>
After peeling off the protective film from the photosensitive transfer material prepared above, under lamination conditions of a roll temperature of 100° C., a linear pressure of 0.8 MPa, and a linear speed of 3.0 m / min, the conductive substrate prepared above, The photosensitive transfer material from which the protective film was removed was pasted together.
A glass mask having a wiring pattern with a line width of 100 μm is brought into close contact with the temporary support without peeling off the temporary support to the laminated photosensitive transfer material, and an exposure machine (M-1S, manufactured by Mikasa Co., Ltd.). was used for exposure.
After left for 1 hour after exposure, the temporary support was peeled off, and a developing solution (28° C., 1.0% potassium carbonate aqueous solution) was sprayed in a shower to remove the uncured portion, thereby producing a resin pattern.
An iron nitrate aqueous solution (30° C., 40.0% by mass) is sprayed onto the conductive substrate having the obtained resin pattern by a shower to remove the metal nanowires contained in the conductive layer where the resin pattern does not exist. did. Further, a 40° C. tetramethylammonium hydroxide (TMAH) aqueous solution (2.38% by mass) was sprayed with a shower to remove the remaining resin pattern, thereby producing a conductive pattern.
The substrate on which the conductive pattern was formed was heat-treated in an infrared oven at 140° C. for 30 minutes to prepare a substrate (wiring substrate) having a conductive pattern (wiring pattern).

<Inspection of voids>
In the wiring pattern obtained, the voids existing in 100 μm square are observed with a scanning electron microscope from the direction perpendicular to the surface direction (thickness direction) of the substrate in the portion where the wiring pattern does not exist (the portion where the metal nanowires are removed). did. The voids in the observed image were binarized, and the ratio of the number of pixels in the observation field was defined as the void ratio. Observations were made at three different locations on the sample, and the average value was taken as the porosity of the sample.
A (good) to D (bad) evaluation was made according to the porosity as follows. As a wiring board, evaluation C or higher is preferable.
A: porosity ≤ 3%
B: 3% < porosity ≤ 5%
C: 5% < porosity ≤ 10%
D: 10% < porosity

<Inspection of pattern abnormality after energization (dimensional stability of conductive pattern after energization)>
Electrodes were connected to terminal portions of the obtained wiring pattern, placed in a constant temperature bath at 85% RH and 85° C., and a direct current (DC) voltage of 10 V was applied for 600 minutes. After the application, the wiring pattern was observed, and the rate of change in pattern width compared with that before the application was rated as A (good) to D (bad) as follows. As a wiring board, evaluation C or higher is preferable.
A: Pattern width change rate <15%
B: 15% ≤ pattern width change rate < 20%
C: 20% ≤ pattern width change rate < 25%
D: 25% ≤ pattern width change rate

<Inspection of void depth>
Of the resulting wiring pattern, the portion where the wiring pattern exists (the portion where the metal nanowires have not been removed) was measured using an atomic force microscope (AFM) by 100 μm from the direction perpendicular to the surface direction of the substrate (thickness direction). Rv was obtained from the roughness curve obtained by measuring in ^two sections. Observations were made at three different locations on the sample, and the average value was taken as Rv1 for that sample.
On the other hand, a portion where the wiring pattern did not exist (a portion where the metal nanowires were removed) was similarly subjected to roughness measurement by AFM, and portions where Rv was 10 nm or more larger than Rv1 were regarded as voids. The number of voids in a 100 square micron section was counted, and the average value of voids at three different locations on the sample was taken as the number of voids (number/100 μm ² ) of the sample.

(Example 15)
A substrate having a conductive pattern was produced and evaluated in the same manner as in Example 1, except that no protective layer was provided.

(Example 16)
A substrate having a conductive pattern was produced and evaluated in the same manner as in Example 2, except that heating was not performed after forming the wiring pattern.

(Example 17)
On a polyimide film (TORMED (registered trademark) Type S manufactured by I.S.T Co., Ltd.), ink containing silver nanoparticles and resin (DNS-0163I, manufactured by Daicel Co., Ltd.) is applied by an inkjet method to a dry film thickness of 0.05 μm. and baked at 120° C. for 30 minutes to form a conductive substrate.
Protective layer forming composition 1 used in Example 1 was coated on the conductive substrate so as to have a film thickness of 40 nm after drying. After drying in an oven at 100° C., exposure was performed at an exposure dose of 600 mJ/cm ² using an exposure machine (M-1S, manufactured by Mikasa Co., Ltd.). Further, post-baking was performed in a convection oven at 140° C. for 30 minutes to form a protective layer (resin layer b).
After peeling off the protective film from the same photosensitive transfer material as in Example 1, under the lamination conditions of a roll temperature of 100° C., a linear pressure of 0.8 MPa, and a linear speed of 3.0 m / min, the conductive substrate prepared above was , the photosensitive transfer material from which the protective film was peeled off was pasted together.
A glass mask having a wiring pattern with a line width of 100 μm is brought into close contact with the temporary support without peeling off the temporary support to the laminated photosensitive transfer material, and an exposure machine (M-1S, manufactured by Mikasa Co., Ltd.). was used for exposure.
After left for 1 hour after exposure, the temporary support was peeled off, and a developing solution (28° C., 1.0% potassium carbonate aqueous solution) was sprayed in a shower to remove the uncured portion, thereby producing a resin pattern.
An aqueous solution of iron nitrate (30° C., 40.0% by mass) is sprayed onto the conductive substrate having the obtained resin pattern by a shower to remove the silver nanoparticles contained in the conductive layer in the portion where the resin pattern does not exist. Removed. Further, a 40° C. tetramethylammonium hydroxide (TMAH) aqueous solution (2.38% by mass) was sprayed with a shower to remove the remaining resin pattern, thereby producing a conductive pattern. Finally, heat treatment was performed in an infrared oven at 140° C. for 30 minutes to produce a substrate (wiring substrate) having a conductive pattern (wiring pattern).
Evaluation was carried out in the same manner as in Example 1.

(Example 18)
On a cycloolefin polymer film (ZeonorFilm (registered trademark) ZB manufactured by Nippon Zeon Co., Ltd.), ink containing copper nanoparticles and resin (IJ-02A, manufactured by Ishihara Chemical Co., Ltd.) is applied so that the dry film thickness is 0.05 μm. Then, it was baked for 30 minutes using a xenon flash lamp to form a conductive substrate.
Protective layer forming composition 1 used in Example 1 was coated on the conductive substrate so as to have a film thickness of 40 nm after drying. After drying in an oven at 100° C., exposure was performed at an exposure dose of 600 mJ/cm ² using an exposure machine (M-1S, manufactured by Mikasa Co., Ltd.). Further, post-baking was performed in a convection oven at 140° C. for 30 minutes to form a protective layer (resin layer b).
After peeling off the protective film from the same photosensitive transfer material as in Example 1, under the lamination conditions of a roll temperature of 100° C., a linear pressure of 0.8 MPa, and a linear speed of 3.0 m / min, the conductive substrate prepared above was , the photosensitive transfer material from which the protective film was peeled off was pasted together.
A glass mask having a wiring pattern with a line width of 100 μm is brought into close contact with the temporary support without peeling off the temporary support to the laminated photosensitive transfer material, and an exposure machine (M-1S, manufactured by Mikasa Co., Ltd.). was used for exposure.
After left for 1 hour after exposure, the temporary support was peeled off, and a developing solution (28° C., 1.0% potassium carbonate aqueous solution) was sprayed in a shower to remove the uncured portion, thereby producing a resin pattern.
A 1 L copper etchant was prepared by dissolving cupric chloride dihydrate (5 g), 28% aqueous ammonia (12 g) and ammonium chloride (8 g) in water. The copper etchant was sprayed onto the obtained conductive substrate having a resin pattern by a shower to remove the copper nanoparticles contained in the conductive layer in the portion where the resin pattern did not exist. Further, a 40° C. tetramethylammonium hydroxide (TMAH) aqueous solution (2.38% by mass) was sprayed with a shower to remove the remaining resin pattern, thereby producing a conductive pattern. Finally, heat treatment was performed in an infrared oven at 140° C. for 30 minutes to produce a substrate (wiring substrate) having a conductive pattern (wiring pattern).
Evaluation was carried out in the same manner as in Example 1.

<Measurement of film thickness>
In Examples 1 to 18, the average film thickness of the conductive pattern and the average film thickness of the resin portion from which the metal nano-body was removed were measured. In any of the examples, the range was 0.90≦the average film thickness of the conductive pattern/the average film thickness of the resin portion from which the metal nano-body was removed≦1.11.

(Comparative example 2)
<Preparation of conductive substrate>
A film (ClearOhm, manufactured by Cambrios) was prepared by laminating a conductive layer in which metal nanowires were dispersed in a resin on a substrate made of a polyethylene terephthalate film.

<Formation of Wiring Pattern>
After peeling off the protective film from the photosensitive transfer material described above, the protective film was peeled off from the conductive substrate under lamination conditions of a roll temperature of 100° C., a linear pressure of 0.8 MPa, and a linear speed of 3.0 m/min. A photosensitive transfer material was laminated.
A glass mask having a wiring pattern with a line width of 100 μm is brought into close contact with the temporary support without peeling off the temporary support, and an exposure machine (M-1S, manufactured by Mikasa Co., Ltd.) is applied to the laminated photosensitive transfer material. was used for exposure.
After left for 1 hour after exposure, the temporary support was peeled off, and a developer (28° C., 1.0% potassium carbonate aqueous solution) was sprayed in a shower to remove the uncured portion, thereby producing a resin pattern.
An iron nitrate aqueous solution (30° C., 40.0% by mass) was sprayed onto the obtained sample by a shower to remove the metal nanowires contained in the conductive layer where the resin pattern did not exist. Further, a TMAH aqueous solution (2.38% by mass) at 40° C. was sprayed with a shower to remove the remaining resin pattern, thereby producing a substrate having a conductive pattern.
Evaluation was carried out in the same manner as in Example 1.

Table 2 summarizes the evaluation results.

As shown in Table 2, in Examples 1 to 14, it was possible to obtain good wiring patterns with few voids and no pattern abnormalities after energization.
In Example 15, no protective layer was provided, but compared with Comparative Example 2 in which heating was not performed, the number of voids was slightly reduced, and the pattern abnormality after energization was improved. It is presumed that the resin contained in the conductive layer softened during heating after etching and filled the voids.
In Example 16, there were more voids than in Example 2, and the pattern was slightly deteriorated after energization, but the material could be used as a wiring forming material without heating. Although the cause is not clear, A-2, which is the resin used for the protective layer 2, is highly hydrophilic and has a low glass transition temperature Tg, so A-2 swells during the etching process and/or peeling process of wiring formation. It is presumed that this is because the voids were closed to some extent. That is, it is presumed that step 5a was performed in the etching step and/or peeling step of wiring formation.
In Examples 17 and 18, a substrate having a conductive pattern was produced by changing the method of producing a conductive substrate. The substrates having the conductive patterns of Examples 17 and 18 had more voids than those of Example 1 and the pattern was slightly deteriorated after energization, but they were sufficiently usable as wiring forming materials.

11: temporary support, 12: transfer layer, 13: thermoplastic resin layer, 15: water-soluble resin layer, 17: photosensitive resin layer, 19: protective film, 20: photosensitive transfer material, GR: light shielding portion (non image area), EX: exposure area (image area), DL: alignment alignment frame

Claims (32)

Step 1a of forming a conductive layer a containing a metal nanobody and a resin 1 on a substrate;
Step 1b of forming a resin layer b containing a resin 2 on the conductive layer a;
step 2a of forming a photosensitive resin layer c on the resin layer b;
step 3 of obtaining a resin pattern c′ of the photosensitive resin layer by exposing and developing the photosensitive resin layer c;
Step 4 of removing the metal nano-body in the conductive layer a by etching to form a conductive pattern d;
A method for manufacturing a substrate having a conductive pattern, including a step 5a of softening or swelling at least one of the resin 1 and the resin 2. Step 1a of forming a conductive layer a containing a metal nanobody and a resin 1 on a substrate;
Step 2b of forming a photosensitive resin layer c on the conductive layer a;
step 3 of obtaining a resin pattern c′ of the photosensitive resin layer by exposing and developing the photosensitive resin layer c;
Step 4 of removing the metal nano-body in the conductive layer a by etching to form a conductive pattern d;
A method for manufacturing a substrate having a conductive pattern, including a step 5b of softening or swelling the resin 1. At least one surface of the obtained substrate having the conductive pattern has a first section with the conductive pattern d formed thereon and a second section without the conductive pattern d formed thereon,
2. The area where voids are observed when the second section is observed with a scanning electron microscope from the thickness direction of the substrate is 10% or less of the total area of the second section or A method of manufacturing a substrate having the conductive pattern according to claim 2 . 4. The area in which voids are observed when observing the second section with a scanning electron microscope from the thickness direction of the substrate is 8% or less of the total area of the second section. A method for manufacturing a substrate having the conductive pattern described. 5. The area in which voids are observed when observing the second section with a scanning electron microscope from the thickness direction of the substrate is 5% or less of the total area of the second section. A method for manufacturing a substrate having the conductive pattern described. 6. The method for producing a substrate having a conductive pattern according to any one of claims 1 to 5, wherein the conductive layer a has a transmittance of 70% or more for light with a wavelength of 380 nm to 780 nm. The method for producing a substrate having a conductive pattern according to any one of claims 1 to 6, wherein the metal nanobody is a metal nanowire. The production of a substrate having a conductive pattern according to any one of claims 1 to 7, wherein the metal nanobody is a nanoparticle having an aspect ratio of 1:1 to 1:10 and an equivalent spherical diameter of 1 nm to 200 nm. Method. The method for producing a substrate having a conductive pattern according to any one of claims 1 to 8, wherein the metal nanobody is a silver or silver compound nanobody. Manufacturing a substrate having a conductive pattern according to any one of claims 1 to 9, wherein a conductive pattern d' is further formed on the surface of the substrate opposite to the surface on which the conductive layer a is provided. Method. 2. The method of manufacturing a substrate having a conductive pattern according to claim 1, wherein the resin layer b contains a compound e capable of bonding or coordinating with the metal contained in the metal nano-body. 12. The method of manufacturing a substrate having a conductive pattern according to claim 11, wherein the compound e is a compound having a lone pair of electrons. 13. Manufacturing a substrate having a conductive pattern according to claim 12, wherein the compound e is at least one compound selected from the group consisting of a nitrogen-containing compound having a lone pair of electrons and a sulfur-containing compound having a lone pair of electrons. Method. The method for producing a substrate having a conductive pattern according to any one of claims 1 to 13, wherein the photosensitive resin layer c contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. 14. The method for producing a substrate having a conductive pattern according to any one of claims 1 to 13, wherein the photosensitive resin layer c contains a resin whose polarity changes under the action of acid and a photoacid generator. The method for producing a substrate having a conductive pattern according to any one of claims 1 to 13, wherein the photosensitive resin layer c contains a resin having a structural unit having a phenolic hydroxyl group and a quinonediazide compound. 17. The method for manufacturing a substrate having a conductive pattern according to any one of claims 1 to 16, wherein the photosensitive resin layer c is formed of a photosensitive transfer material. 18. The method for producing a substrate having a conductive pattern according to any one of claims 1 to 17, further comprising an intermediate layer on the photosensitive resin layer c. 2. The conductive pattern according to claim 1, wherein step 5a is a step of softening at least one of said resin 1 and said resin 2 by heat treatment and filling the voids generated by removing said metal nano-body by said etching. A method of manufacturing a substrate having: 20. The method of manufacturing a substrate having a conductive pattern according to claim 19, wherein the heat treatment in step 5a is performed at a heating temperature that satisfies Tgp<Th<Tgb.
Note that Th represents the maximum temperature (° C.) during the heat treatment in step 5a, Tgp represents the lower temperature (° C.) of the glass transition temperature of resin 1 and the glass transition temperature of resin 2, and Tgb represents the substrate. represents the glass transition temperature (°C) of 3. The method of manufacturing a substrate having a conductive pattern according to claim 2, wherein step 5b is a step of softening the resin 1 by heat treatment and filling the voids generated by the removal of the metal nano-body by the etching. Step 5a is a step of swelling at least one of the resin 1 and the resin 2 during or after the step 4 and filling the voids generated by the removal of the metal nano-body by the etching. Item 1. A method for manufacturing a substrate having a conductive pattern according to item 1. 3. The conductive pattern according to claim 2, wherein the step 5b is a step of swelling the resin 1 during or after the step 4 and filling a gap generated by removing the metal nano-body by the etching. A method for manufacturing a substrate having A method for manufacturing an electronic device comprising a substrate having a conductive pattern obtained by the method for manufacturing a substrate having a conductive pattern according to any one of claims 1 to 23. a substrate;
On at least one surface of the substrate, a first section in which a conductive pattern d containing a metal nanobody and a resin 1 is formed, and a second section in which the conductive pattern d is not formed,
The area where voids are observed when the second section is observed with a scanning electron microscope from the thickness direction of the substrate is 10% or less of the total area of the second section. substrate. 26. The substrate having a conductive pattern according to claim 25, wherein said resin 1 is present in said second section. 0.90≦H1/H2≦1.11, where H1 is the layer thickness of the first section from the substrate surface, and H2 is the layer thickness of the second section from the substrate surface. 27. A substrate having a conductive pattern according to claim 26. 28. The substrate having a conductive pattern according to claim 26 or 27, wherein the number of recesses having a depth of 10 nm or more in the second section is 10/100 m2 ^{or less} . A protective film for a metal nanobody, having a resin layer containing a resin having a glass transition temperature of 150° C. or lower. The metal nanobody according to claim 29, wherein the resin having a glass transition temperature of 150°C or less includes at least one resin selected from the group consisting of acrylic resins, polyester resins, polyvinyl acetal resins, and phenolic resins. Protective film for The group in which the resin layer comprises an oxime ester photopolymerization initiator, a biimidazole photopolymerization initiator, an alkylphenone photopolymerization initiator, an acetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. 31. The protective film for metal nano-body according to claim 29 or 30, further comprising at least one polymerization initiator selected from. 32. The protective film for metal nano-body according to any one of claims 29 to 31, wherein the resin layer further contains a polymerizable compound having a functionality of two or more.

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