CN116149134A - Method for producing resin pattern, method for producing conductive pattern, and laminate - Google Patents

Abstract

The invention provides a method for manufacturing a resin pattern with improved adhesion between a conductive layer and a photosensitive resin layer and a related technology, wherein the method for manufacturing the resin pattern sequentially comprises the following steps: a step of preparing a laminate including a substrate and a conductive layer having a 1 st surface facing the substrate and a 2 nd surface opposite to the 1 st surface; a step of forming a photosensitive resin layer on the 2 nd surface of the conductive layer, the photosensitive resin layer having a 3 rd surface facing the conductive layer and a 4 th surface opposite to the 3 rd surface; a step of exposing the photosensitive resin layer to a pattern; and developing the photosensitive resin layer to form a resin pattern, wherein the conductive layer contains a metal nanomaterial and a resin, and the surface free energy γs1 of the 2 nd surface of the conductive layer and the surface free energy γr of the 3 rd surface of the photosensitive resin layer satisfy the relationship of |γs1- γr|12 or less.

Description

Method for producing resin pattern, method for producing conductive pattern, and laminate

Technical Field

The present invention relates to a method for producing a resin pattern, a method for producing a conductive pattern, and a laminate.

Background

For example, a conductive pattern suitable for an article such as a touch panel is formed by etching a conductive layer. For example, patent document 1 below discloses a method of etching a layer containing silver nanowires using a patterned insulating layer as a mask.

Patent document 1: taiwan area patent application publication No. 201629992 specification

As the etching mask, for example, a resin pattern is given. For example, the resin pattern is formed by exposing and developing a photosensitive resin layer disposed on the conductive layer. However, the adhesion between the photosensitive resin layer and the conductive layer is sometimes insufficient. In particular, adhesion between the photosensitive resin layer and the conductive layer containing the metal nanomaterial tends to be reduced. For example, a decrease in adhesion between the photosensitive resin layer and the conductive layer may result in a decrease in resolution when patterning.

Disclosure of Invention

An object of an embodiment of the present invention is to provide a method for producing a resin pattern in which adhesion between a conductive layer and a photosensitive resin layer is improved.

Another object of the present invention is to provide a method for producing a conductive pattern, in which adhesion between a conductive layer and a photosensitive resin layer is improved.

Another object of another embodiment of the present invention is to provide a laminate including a conductive layer that exhibits excellent adhesion to a photosensitive resin layer.

The present invention includes the following means.

<1> a method for producing a resin pattern, comprising, in order: a step of preparing a laminate including a substrate and a conductive layer having a 1 st surface facing the substrate and a 2 nd surface opposite to the 1 st surface; a step of forming a photosensitive resin layer on the 2 nd surface of the conductive layer, the photosensitive resin layer having a 3 rd surface facing the conductive layer and a 4 th surface opposite to the 3 rd surface; a step of exposing the photosensitive resin layer to a pattern; and developing the photosensitive resin layer to form a resin pattern, wherein the conductive layer contains a metal nanomaterial and a resin, and the surface free energy γs1 of the 2 nd surface of the conductive layer and the surface free energy γr of the 3 rd surface of the photosensitive resin layer satisfy the relationship of |γs1- γr|12 or less.

<2> the method for producing a resin pattern according to <1>, wherein the surface free energy γs1 and the surface free energy γr satisfy the relationship of |γs1 to γr|+.3.

<3> the method for producing a resin pattern according to <1> or <2>, wherein the resin contains an acrylic resin.

<4> the method for producing a resin pattern according to any one of <1> to <3>, wherein the conductive layer is a layer formed by bringing a solution containing an organic substance and a solvent into contact with the conductive layer (a) containing the metal nanomaterial and the resin (a).

<5> the method for producing a resin pattern according to <4>, wherein the resin (A) contains a cellulose derivative.

<6> the method for producing a resin pattern according to any one of <1> to <5>, wherein the metal nanomaterial is silver nanowires.

<7> the method for producing a resin pattern according to any one of <1> to <6>, wherein the photosensitive resin layer contains an alkali-soluble resin, a polymerizable compound and a photopolymerization initiator.

<8> the method for producing a resin pattern according to any one of <1> to <6>, wherein the photosensitive resin layer contains a resin whose polarity is changed by an acid and a photoacid generator.

<9> the method for producing a resin pattern according to any one of <1> to <6>, wherein the photosensitive resin layer contains a resin having a phenolic hydroxyl group and a quinone diazide derivative.

<10> the method for producing a resin pattern according to any one of <1> to <9>, wherein the photosensitive resin layer contains a heterocyclic compound.

<11> the method for producing a resin pattern according to any one of <1> to <10>, wherein the step of forming the photosensitive resin layer comprises: a step of preparing a transfer material including a temporary support and the photosensitive resin layer; and adhering the photosensitive resin layer of the transfer material to the conductive layer.

<12> a method for producing a conductive pattern, comprising, in order: a step of forming a resin pattern by the method for producing a resin pattern according to any one of <1> to <11 >; a step of etching the conductive layer using the resin pattern as a mask to form a conductive pattern; and removing the resin pattern.

<13>A laminate, comprising: a substrate; and a conductive layer having a 1 st surface facing the substrate and a 2 nd surface opposite to the 1 st surface, wherein the conductive layer contains a metal nanomaterial and a resin, and the 2 nd surface of the conductive layer has a surface free energy γs1 of 38mJ/m ² ～50mJ/m ² 。

<14> a laminate, comprising: a substrate; and a conductive layer having a 1 st surface facing the substrate and a 2 nd surface opposite to the 1 st surface, wherein the conductive layer contains a metal nanomaterial and a resin, and a contact angle of distilled water with respect to the 2 nd surface of the conductive layer is 50 DEG to 85 deg.

Effects of the invention

According to one embodiment of the present invention, there is provided a method for producing a resin pattern in which adhesion between a conductive layer and a photosensitive resin layer is improved.

According to another embodiment of the present invention, there is provided a method for producing a conductive pattern in which adhesion between a conductive layer and a photosensitive resin layer is improved.

According to another embodiment of the present invention, there is provided a laminate including a conductive layer exhibiting excellent adhesion to a photosensitive resin layer.

Drawings

Fig. 1 is a schematic diagram of a preparation step and a photosensitive resin layer forming step in a method for manufacturing a resin pattern according to an embodiment.

Fig. 2 is a schematic diagram of a preparation step and a photosensitive resin layer forming step in a method for manufacturing a resin pattern according to an embodiment.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the present invention.

When the embodiments of the present invention are described with reference to the drawings, the description of the constituent elements and symbols repeated in the drawings may be omitted. Unless otherwise specified, constituent element representations in the drawings using the same reference numerals are identical constituent elements. The dimensional ratios in the drawings do not necessarily represent actual dimensional ratios.

In the present invention, the numerical range indicated by "to" is a range including the numerical values before and after "to" as the lower limit value and the upper limit value. In the numerical ranges described in stages in the present invention, the upper limit or the lower limit described in a certain numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. In the numerical ranges described in the present invention, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value described in the embodiment.

In the present invention, "(meth) acrylic" means acrylic acid, methacrylic acid or both acrylic acid and methacrylic acid.

In the present invention, "(meth) acrylate" means acrylate, methacrylate or both acrylate and methacrylate.

In the present invention, when a plurality of substances corresponding to a certain component are present in an object, unless otherwise specified, the content of the component represents the total amount of the plurality of substances present in the object.

In the present invention, the term "process" includes not only an independent process but also a process which cannot be clearly distinguished from other processes as long as the intended purpose can be achieved.

In the present invention, the expression of the unsubstituted and substituted groups (atomic groups) includes groups having substituents and groups having no substituents. For example, the term "alkyl" includes alkyl groups having substituents (i.e., substituted alkyl groups) and alkyl groups having no substituents (i.e., unsubstituted alkyl groups).

In the present invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

In the present invention, a combination of two or more preferred modes is a more preferred mode.

In the present invention, the chemical structural formula is sometimes described as a simplified structural formula in which a hydrogen atom is omitted.

In the present invention, "solid component" means a component other than a solvent.

In the present invention, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene-equivalent molecular weights measured using a Gel Permeation Chromatography (GPC) analysis apparatus. In the measurement of the above molecular weight, as the column, "TSKgel GMHxL, TSKgel G4000HxL" (TOSOH CORPORATION) and "TSKgel G2000HxL" (TOSOH CORPORATION) were used, as the detector, a differential refractometer was used, and as the solvent, tetrahydrofuran (THF) was used.

In the present invention, the term "molecular weight" as used for a compound having a molecular weight distribution means a weight average molecular weight unless otherwise specified.

In the present invention, unless otherwise specified, the composition ratio of the structural units of the polymer means the mass ratio.

In the present invention, ordinal words (for example, "1 st" and "2 nd") are terms for distinguishing constituent elements, and do not limit the number of constituent elements or the merits and merits of the constituent elements.

< method (1) for producing resin Pattern >

The method for producing a resin pattern according to an embodiment of the present invention includes the following (1) to (4) in order.

(1) A step of preparing a laminate including a substrate and a conductive layer having a 1 st surface facing the substrate and a 2 nd surface opposite to the 1 st surface (hereinafter, sometimes referred to as a "preparation step").

(2) And a step of forming a photosensitive resin layer on the 2 nd surface of the conductive layer, the photosensitive resin layer having a 3 rd surface facing the conductive layer and a 4 th surface opposite to the 3 rd surface (hereinafter, sometimes referred to as "photosensitive resin layer forming step").

(3) A step of exposing the photosensitive resin layer to a pattern (hereinafter, sometimes referred to as an "exposure step").

(4) A step of developing the photosensitive resin layer to form a resin pattern (hereinafter, sometimes referred to as a "developing step").

In the above embodiment, the conductive layer contains a metal nanomaterial and a resin. In the above embodiment, the surface free energy γs1 of the 2 nd surface of the conductive layer and the surface free energy γr of the 3 rd surface of the photosensitive resin layer satisfy the relationship of |γs1—γr|+.12.

According to the above embodiment, a method for producing a resin pattern is provided in which adhesion between a conductive layer and a photosensitive resin layer is improved. The reason why the adhesion between the conductive layer and the photosensitive resin layer is improved is assumed to be that the difference between the surface free energy γs1 of the 2 nd surface of the conductive layer and the surface free energy γr of the 3 rd surface of the photosensitive resin layer is reduced.

[ preparation procedure ]

In the preparation step, a laminate including a substrate and a conductive layer is prepared. The conductive layer has a 1 st surface facing the substrate and a 2 nd surface opposite to the 1 st surface.

In the present invention, "preparing a laminate" means making the laminate usable. The laminate may be a prefabricated laminate. The laminate may be produced in a preparation process.

(substrate)

The laminate in the preparation step includes a substrate.

Examples of the component of the substrate include resins and inorganic substances. Examples of the resin include polyesters (for example, polyethylene terephthalate and polyethylene naphthalate), polyether ether ketone, acrylic resins, cycloolefin polymers, polycarbonates, and polyimides. Examples of the inorganic substance include glass and quartz.

The substrate is preferably a resin film having high transparency, and more preferably a polyethylene terephthalate film, a polyethylene naphthalate film, a cycloolefin polymer film, or a transparent polyimide.

The substrate is preferably a substrate having a region transparent to the exposure wavelength. In the present invention, the "region transparent to the exposure wavelength" means a region having a transmittance of 30% or more of the dominant wavelength in the exposure wavelength. The "dominant wavelength" means the wavelength with the strongest intensity among the exposure wavelengths. The transmittance is preferably 50% or more, more preferably 60% or more, further preferably 80% or more, and particularly preferably 90% or more. The upper limit of the transmittance is not limited. The transmittance is determined, for example, in a range of 100% or less. The transmittance is measured using a known transmittance measuring instrument (for example, V-700series manufactured by JASCO Corporation). The region transparent to the exposure wavelength may be disposed over the entire substrate or a portion of the substrate. The region transparent to the exposure wavelength is preferably arranged at a portion corresponding to the exposure portion in the exposure step. The region transparent to the exposure wavelength is preferably disposed over the entire substrate. That is, the substrate is preferably a substrate transparent to the exposure wavelength.

The thickness of the substrate is not limited. The average thickness of the substrate is preferably 10 μm to 100 μm, more preferably 10 μm to 60 μm, from the viewpoints of transport property, electrical property and film forming property. The average thickness of the substrate was obtained by arithmetically averaging the thicknesses at 10 points of the substrate. The thickness of the substrate was measured by observing a cross section of the substrate using a Scanning Electron Microscope (SEM).

(conductive layer)

The laminate in the preparation step includes a conductive layer. The conductive layer has a 1 st surface facing the substrate and a 2 nd surface opposite to the 1 st surface.

In the present invention, "conductivity" means sheet resistivity of less than 1000Ω/≡. The sheet resistivity is preferably less than 200Ω/≡. In the present invention, sheet resistivity is measured using a known resistivity meter (e.g., resistance measuring devices EC-80P, NAPSON CORPORATION). The sheet resistivity of the non-layered object is measured by forming a layered sample equivalent to the non-layered object.

The conductive layer contains a metal nanomaterial and a resin.

In the present invention, "metal nanomaterial" means a metal material having a size of a nanometer scale (for example, at least one dimension is 1nm to 1,000 nm).

Examples of the component of the metal nanomaterial include copper, silver, zinc, iron, chromium, molybdenum, nickel, aluminum, gold, platinum, and palladium. The metal nanomaterial may contain a single metal. The metal nanomaterial may also contain an alloy. Examples of the component of the metal nanomaterial include Indium Tin Oxide (ITO) and Indium zinc Oxide (Indium Zinc Oxide:IZO). The metal nanomaterial preferably contains copper, silver, nickel, aluminum, gold, platinum, palladium, or an alloy thereof, more preferably contains silver or a silver alloy, and even more preferably contains silver.

The metal nanomaterial is preferably a metal nanowire. The metal nanowires can improve the transparency of the conductive layer. Examples of the metal nanowire include silver nanowires, copper nanowires, gold nanowires, and platinum nanowires. The metal nanomaterial is preferably silver nanowires from the viewpoint of conductivity and transparency.

Examples of the shape of the metal nanowire include a cylinder and a rectangular parallelepiped. Examples of the shape of the metal nanowire include a columnar shape having a polygonal cross section. The cross-sectional shape of the metal nanowires is observed, for example, using a Transmission Electron Microscope (TEM).

From the viewpoint of transparency, the average diameter (so-called short axis length) of the metal nanowires is preferably 50nm or less, more preferably 40nm or less, and further preferably 30nm or less. The average diameter of the metal nanowires is preferably 5nm or more from the viewpoint of oxidation resistance and durability. The average diameter of the metal nanowires is determined using a Transmission Electron Microscope (TEM) or an optical microscope. Specifically, the diameters of 300 metal nanowires randomly selected from among a plurality of metal nanowires observed using a Transmission Electron Microscope (TEM) or an optical microscope were measured. The arithmetic average of the measured values was taken as the average diameter of the metal nanowires.

From the viewpoint of conductivity, the average length (so-called long axis length) of the metal nanowires is preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 30 μm or more. The average length of the metal nanowire is preferably 1mm or less from the viewpoint of suppressing the formation of aggregates in the production process of the metal nanowire. The average length of the metal nanowires is determined using a Transmission Electron Microscope (TEM) or an optical microscope. Specifically, the lengths of 300 metal nanowires randomly selected from among a plurality of metal nanowires observed using a Transmission Electron Microscope (TEM) or an optical microscope were measured. The arithmetic average of the measured values was taken as the average length of the metal nanowires.

The metal nanomaterial may be a metal nanoparticle. Examples of the metal nanoparticles include silver nanoparticles, copper nanoparticles, gold nanoparticles, and platinum nanoparticles. The metal nanoparticles are preferably silver nanoparticles from the viewpoint of conductivity and transparency.

The metal nanoparticles may be spherical particles in morphology. The metal nanoparticles may be in the form of plate-like particles. The metal nanoparticles may be irregularly shaped particles.

The average primary particle diameter of the metal nanoparticles is preferably 0.1nm to 500nm, more preferably 1nm to 200nm, and even more preferably 1nm to 100nm from the viewpoints of stability and fusion temperature. The average primary particle diameter of the metal nanoparticles was determined by the following method: the particle diameters of 100 particles were measured using a scanning electron microscope (e.g., S-3700N, hitachi High-Tech Corporation) and an image processing measuring device (e.g., LUZEXAP, NIRECO CORPORATION), and the measured values were arithmetically averaged. In the present invention, "particle diameter" means the equivalent circle diameter of particles. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the object.

From the viewpoints of dispersibility and conductivity, the metal nanomaterial is preferably particles having an aspect ratio of 1:1 to 1:10 and an average primary particle diameter of 1nm to 200 nm.

From the viewpoint of conductivity, the metal nanoparticles preferably contain a metal having a standard electrode potential higher than that of silver (hereinafter, sometimes referred to as "metal noble than silver"). Examples of the noble metal than silver include gold. The metal nanoparticles preferably comprise flat particles coated with gold. The gold coats at least a portion of the flat particles.

In the metal nanoparticle, the ratio of the content of the metal noble than silver to the content of silver is preferably 0.01 atomic% to 5 atomic%, more preferably 0.1 atomic% to 2 atomic%, and still more preferably 0.2 atomic% to 0.5 atomic%. The content of a metal noble than silver is measured by high-frequency inductively coupled plasma (Inductively Coupled Plasma: ICP) emission spectrometry, for example, after a sample is dissolved by an agent such as an acid.

The conductive layer may contain one or two or more kinds of metal nanomaterial.

The ratio of the content of the metal nanomaterial to the total mass of the conductive layer is preferably 1 to 99 mass%, more preferably 1 to 95 mass%, and even more preferably 1 to 90 mass% from the viewpoints of conductivity and transparency.

From the viewpoint of durability, the resin is preferably a binder polymer.

Examples of the resin include acrylic resins, polyesters, polycarbonates, polyimides, polyamides, polyolefins, polynorbornenes, cellulose resins, polyvinyl alcohols (PVA), and polyvinylpyrrolidone.

Examples of the acrylic resin include poly (methyl methacrylate).

The acrylic resin is preferably a polymer containing at least one structural unit selected from structural units derived from acrylic esters and structural units derived from methacrylic esters.

Examples of the polyester include polyethylene terephthalate (PET).

Examples of the polyolefin include polypropylene.

Examples of the cellulose resin include cellulose and cellulose derivatives. Examples of cellulose derivatives include hydroxypropyl methylcellulose (HPMC), hydroxyethyl cellulose (HEC), methylcellulose (MC), hydroxypropyl cellulose (HPC) and carboxymethyl cellulose (CMC).

From the viewpoint of stability of the metal nanomaterial, the resin preferably contains at least one resin selected from the group consisting of an acrylic resin and a cellulose resin, and more preferably contains at least one resin selected from the group consisting of an acrylic resin and a cellulose derivative. From the viewpoint of stability of the metal nanomaterial, the resin preferably contains an acrylic resin. From the viewpoint of stability of the metal nanomaterial, the resin preferably contains a cellulose derivative.

The resin may contain a conductive polymer compound. Examples of the conductive polymer compound include polyaniline and polythiophene.

From the viewpoint of dimensional stability of the conductive pattern after the energization, the glass transition temperature (Tg) of the resin is preferably 180 ℃ or less, more preferably 40 to 160 ℃, and still more preferably 60 to 150 ℃.

In the present invention, the glass transition temperature (Tg) is measured by a method described in "JIS K7121 (1987)" or "JIS K6240 (2011)" using Differential Scanning Calorimetry (DSC). As the glass transition temperature, an extrapolated glass transition onset temperature is employed. Hereinafter, a specific method for measuring the glass transition temperature will be described. First, after the temperature was kept at about 50 ℃ lower than the glass transition temperature of the predicted resin until the device was stable, the device was heated at a heating rate of 20 ℃/min to a temperature about 30 ℃ higher than the temperature at which the glass transition was completed, and a Differential Thermal Analysis (DTA) curve or DSC curve was prepared. Next, the temperature of the intersection point of the straight line extending the low-temperature side base line on the DTA curve or DSC curve to the high-temperature side and the wiring line drawn at the point at which the gradient of the curve of the stepwise change portion of the glass transition becomes maximum (i.e., the extrapolated glass transition start temperature) is obtained.

The conductive layer may contain one or two or more resins.

The ratio of the resin content to the total mass of the conductive layer is preferably 1 to 90 mass%, more preferably 10 to 80 mass%, and even more preferably 20 to 70 mass%.

The conductive layer may also contain other components. Examples of the other component include surfactants. Examples of the surfactant include RADISOL A-90 (NOF CORPORATION, solid content: 1%) and NAROACTY CL-95 (SANYO CHEMICAL INDUSTRIES, LTD., solid content: 1%). Examples of the other component include inorganic particles. Examples of the inorganic particles include silica, mullite and alumina.

The surface free energy γs1 of the 2 nd surface of the conductive layer is preferably 30mJ/m ² ～50mJ/m ² More preferably 32mJ/m ² ～46mJ/m ² Further preferably 38mJ/m ² ～46mJ/m ² . If the surface free energy γs1 of the 2 nd surface of the conductive layer is within the above range, the difference between the surface free energy γs1 of the 2 nd surface of the conductive layer and the surface free energy γr of the 3 rd surface of the photosensitive resin layer is liable to be reduced. As a result, the adhesion between the conductive layer and the photosensitive resin layer can be improved.

In the present invention, the surface free energy of the conductive layer is determined by the contact angle of distilled water and diiodomethane (i.e., CH ₂ I ₂ ) Is calculated by the Owens and Wendt (wewensi and went) method. In the present invention, the contact angle is an average value of contact angles measured 3 times using a contact angle meter (for example, dropmaster500, kyowa Interface Science co., ltd.). The amount of distilled water and diiodomethane added was 3.0. Mu.L. The time from the addition of distilled water and diiodomethane was 20 seconds. The contact angle was measured at 25 ℃.

Examples of the method for adjusting the surface free energy of the conductive layer include surface modification. Examples of the surface modification include corona treatment and plasma treatment. Examples of the surface modification include a surface modification step (i.e., a method using a solution containing an organic substance and a solvent) described later. From the viewpoint of easy adjustment of the surface free energy, the surface free energy of the conductive layer is preferably adjusted by a surface modification step described later. The surface free energy of the conductive layer can be adjusted according to the composition of the conductive layer.

The contact angle of the distilled water with the 2 nd surface of the conductive layer is preferably 50 ° to 85 °, more preferably 50 ° to 75 °, and still more preferably 60 ° to 75 °. If the contact angle of distilled water with respect to the 2 nd surface of the conductive layer is within the above range, the difference between the surface free energy γs1 of the 2 nd surface of the conductive layer and the surface free energy γr of the 3 rd surface of the photosensitive resin layer is liable to decrease. As a result, the adhesion between the conductive layer and the photosensitive resin layer can be improved.

The contact angle of diiodomethane with respect to the 2 nd surface of the conductive layer is preferably 10 ° to 65 °, more preferably 20 ° to 60 °. When the contact angle of diiodomethane with respect to the 2 nd surface of the conductive layer is within the above range, the difference between the surface free energy γs1 of the 2 nd surface of the conductive layer and the surface free energy γr of the 3 rd surface of the photosensitive resin layer is liable to decrease. As a result, the adhesion between the conductive layer and the photosensitive resin layer can be improved.

Examples of the method for adjusting the contact angle of distilled water or diiodomethane to the surface of the conductive layer include the above-mentioned surface modification.

The thickness of the conductive layer is not limited. The average thickness of the conductive layer is preferably 0.001 μm to 1,000 μm, more preferably 0.005 μm to 15 μm, and even more preferably 0.01 μm to 10 μm from the viewpoints of conductivity and film formability. The average thickness of the conductive layer is measured by a method based on the above-described measurement method of the average thickness of the substrate.

The method for producing the conductive layer is not limited. The conductive layer may be manufactured by applying a composition (e.g., ink) containing a metal nanomaterial and a resin onto a substrate. The composition may be a curable composition. The curable composition may be a thermosetting composition. The curable composition may be a photocurable composition. The curable composition may be a thermosetting and photocurable composition. The composition may also contain other ingredients. The composition may also contain a solvent. Examples of the solvent include water and an organic solvent. Examples of the preferable organic solvent include hydrocarbons (e.g., toluene, dodecane, tetradecane, cyclododecene, n-heptane, and n-undecane) and alcohols (e.g., ethanol and isopropanol). Examples of the coating method include an inkjet method, a spray method, a roll coating method, a bar coating method, a curtain coating method, and a die coating method (i.e., a slit coating method). The method for producing the conductive layer may further include other steps (for example, drying and calcination) as needed after the composition is applied.

The conductive layer is preferably a layer formed by bringing a solution containing an organic substance and a solvent into contact with the conductive layer (a) containing a metal nanomaterial and a resin (a). The preparation step may include a step of forming a conductive layer by bringing a solution containing an organic substance and a solvent into contact with the conductive layer (a) containing the metal nanomaterial and the resin (a). The method described above can form a conductive layer having high adhesion to the photosensitive resin layer. Hereinafter, the step of bringing the specific solution into contact with the conductive layer (a) as described above may be referred to as a "surface modification step".

The manner of the metal nanomaterial in the conductive layer (a) is the same as that of the metal nanomaterial in the conductive layer described above.

The ratio of the content of the metal nanomaterial to the total mass of the conductive layer (a) is preferably 1 to 99 mass%, more preferably 1 to 95 mass%, and even more preferably 1 to 90 mass% from the viewpoints of conductivity and transparency.

From the viewpoint of durability, the resin (a) is preferably a binder polymer.

The resin (a) is preferably, for example, an acrylic resin, a polyester, a polycarbonate, a polyimide, a polyamide, a polyolefin, a polynorbornene, a cellulose resin, a polyvinyl alcohol (PVA), or a polyvinylpyrrolidone.

Examples of the acrylic resin include poly (methyl methacrylate).

Examples of the polyester include polyethylene terephthalate (PET).

Examples of the polyolefin include polypropylene.

Examples of the cellulose resin include cellulose and cellulose derivatives. Examples of cellulose derivatives include hydroxypropyl methylcellulose (HPMC), hydroxyethyl cellulose (HEC), methylcellulose (MC), hydroxypropyl cellulose (HPC) and carboxymethyl cellulose (CMC).

From the viewpoints of dispersibility of the metal nanomaterial and dimensional stability of the conductive pattern after being electrified, the resin (a) preferably contains at least one resin selected from cellulose resins, polyvinyl alcohols and polyvinylpyrrolidone, more preferably contains a cellulose resin, and still more preferably contains a cellulose derivative.

The resin (a) may contain a conductive polymer compound. Examples of the conductive polymer compound include polyaniline and polythiophene.

From the viewpoint of dimensional stability of the conductive pattern after the energization, the glass transition temperature (Tg) of the resin (a) is preferably 180 ℃ or less, more preferably 40 to 160 ℃, and still more preferably 60 to 150 ℃.

The conductive layer (a) may contain one or two or more resins (a).

The content of the resin (a) is preferably 1 to 90 mass%, more preferably 10 to 80 mass%, and even more preferably 20 to 70 mass% relative to the total mass of the conductive layer (a).

The conductive layer (a) may further contain other components. Examples of the other component include surfactants. Examples of the surfactant include RAPISOL A-90 (NOP CORPORATION, solid content: 1%) and NAROACTY CL-95 (SANYO CHEMICAL INDUSTRIES, LTD., solid content: 1%). Examples of the other component include inorganic particles. Examples of the inorganic particles include silica, mullite and alumina.

In the solution used in the surface modification step, the organic substance is different from the solvent. I.e. the solvent is excluded from the organics.

Examples of the organic substance include resins. Examples of the resin include an acrylic resin (for example, a DIANAL series manufactured by Mitsubishi Chemical Corporation and a NIPPON shokubac CO., ltd. Manufactured by ACRYSET), a POLYESTER resin (for example, a unicika ltd. Manufactured by elitel series and a Nichigo-POLYESTER series manufactured by Mitsubishi Chemical Corporation), a polyvinyl alcohol resin (for example, a KURARAY CO., ltd. Manufactured by POVAL), a polyvinyl acetal resin (for example, a SEKISUI CHEMICAL CO., ltd. Manufactured by S-LEC series), and a phenol resin (for example, a phenol series manufactured by DIC CO rportion).

From the viewpoint of dimensional stability of the conductive pattern after the energization, the organic substance preferably contains a resin, more 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, and even more preferably contains an acrylic resin. The acrylic resin is preferably a polymer containing at least one structural unit selected from structural units derived from acrylic esters and structural units derived from methacrylic esters. Further, the acrylic resin is preferably a polymer containing at least one structural unit selected from the group consisting of a structural unit derived from benzyl acrylate and a structural unit derived from benzyl methacrylate.

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

The acid value of the resin is preferably 0 to 60mgKOH/g, more preferably 0 to 50mgKOH/g, and even more preferably 0 to 40mgKOH/g, from the viewpoints of etching resistance and dimensional stability of the conductive pattern after being energized.

In the present invention, "acid value" means the mass (mg) of potassium hydroxide required for neutralizing 1g of the sample. The unit of acid value is represented by mgKOH/g. The acid value was measured by the following method. First, a sample was dissolved in a mixed solvent containing tetrahydrofuran and water (volume ratio: tetrahydrofuran/water=9/1). The solution was subjected to neutralization titration using a potentiometric titration apparatus (e.g., AT-510, KYOTO ELECTRONICS MANUFACTURING co., ltd.) with 0.1mol/L aqueous sodium hydroxide solution AT 25 ℃. The acid value was calculated by using the inflection point of the titration pH curve as the titration end point as shown in the following formula.

The formula: a=56.11×vs×0.1×f/w

A: acid value (mgKOH/g)

Vs: the amount of 0.1mol/L aqueous sodium hydroxide solution (mL) required for titration

f: titration rate of 0.1mol/L aqueous sodium hydroxide solution

w: mass (g) of sample converted into solid content

The solution used in the surface modification step may contain one or two or more resins.

From the viewpoint of conductivity, the ratio of the content of the resin to the total mass of the solid components of the solution is preferably 95 mass% or less, more preferably 90 mass% or less, and further preferably 10 mass% or more and 90 mass% or less.

The organic matter may contain resins and other components. Examples of the other component include a polymerizable compound and a polymerization initiator. For example, the organic material may contain a resin, a polymerizable compound, and a polymerization initiator.

The number of polymerizable groups in the polymerizable compound is preferably 2 or more, more preferably 3 to 10, and still more preferably 4 to 8.

The polymerizable compound is preferably an ethylenically unsaturated compound, more preferably a (meth) acrylate compound. The polymerizable compound is preferably a compound having two or more ethylenically unsaturated groups, more preferably a compound having two or more (meth) acryloyl groups.

The polymerizable compound may be selected from polymerizable compounds described as components of the photosensitive resin layer described later.

The solution used in the surface modification step may contain one or two or more kinds of polymerizable compounds.

From the viewpoint of conductivity, the ratio of the content of the resin to the total mass of the solid components of the solution is preferably 95 mass% or less, more preferably 90 mass% or less, and further preferably 10 mass% or more and 90 mass% or less.

The polymerization initiator is preferably a photopolymerization initiator. Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having a bisimidazole structure, a photopolymerization initiator having an α -aminoalkylbenzophenone structure, a photopolymerization initiator having an α -hydroxyalkylbenzophenone structure, a photopolymerization initiator having an acetophenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure.

The polymerization initiator preferably contains at least one kind of photopolymerization initiator selected from the group consisting of a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having a bisimidazole structure, a photopolymerization initiator having an α -aminoalkylbenzophenone structure, a photopolymerization initiator having an α -hydroxyalkylbenzophenone structure, a photopolymerization initiator having an acetophenone structure, and a photopolymerization initiator having an acylphosphine oxide structure, and more preferably contains a photopolymerization initiator having an oxime ester structure.

The solution used in the surface modification step may contain one or two or more polymerization initiators.

From the viewpoint of conductivity, the ratio of the content of the polymerization initiator to the total mass of the solid components of the solution is preferably 0.1 to 20 mass%, more preferably 0.1 to 10 mass%, and even more preferably 0.1 to 5 mass%.

The solution used in the surface modification step may contain one or two or more organic substances.

Examples of the solvent include water and an organic solvent. The solvent preferably contains an organic solvent. Examples of the organic solvent include alkylene glycol ethers, alkylene glycol ether acetates (e.g., propylene glycol monomethyl ether acetate), alcohols (e.g., methanol and ethanol), ketones (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbons (e.g., toluene), aprotic polar solvents (e.g., N-dimethylformamide), cyclic ethers (e.g., tetrahydrofuran), esters, amides, and lactones.

The solution used in the surface modification step may contain one or two or more solvents.

The solution used in the surface modification step may contain other components than those described above.

Examples of the other components include ultraviolet absorbers, antioxidants, light stabilizers, rust inhibitors, surfactants, viscosity modifiers, preservatives, sensitizers, polymerization inhibitors, plasticizers, metal oxide particles, dispersants, acid proliferation agents, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators other than photopolymerization initiators, thermal acid generators, crosslinking agents, and organic or inorganic anti-settling agents. These components may contain only 1 kind, or may contain 2 or more kinds of raw materials having various functions at the same time.

For example, the solution used in the surface modification step may contain an antioxidant. Examples of the antioxidant include phosphate antioxidants, phenol antioxidants, and thioether antioxidants.

For example, the solution used in the surface modification step may contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and benzoate-based ultraviolet absorbers.

For example, the solution used in the surface modification step may contain an anti-rust agent. Examples of the rust inhibitor include nitrogen-containing compounds, sulfur-containing compounds, heterocyclic compounds, fatty acids, amine salts, fatty acid esters, surfactants, chelate-forming compounds, and the like. Specifically, compounds such as triazole, imidazole, pyrazole, pyridine, tetrazole, oxazole, thiophene, thiadiazole, dithiazole, morpholine, oxazine, thiomorpholine, triamine, benzotriazole, benzimidazole, dodecyl mercaptan, naphthalene mercaptan, cysteine, methionine, thiophenol, oleic acid, dimer acid, naphthenic acid, glycidyl ester of higher fatty acid, sorbitol monoisostearate, ethylenediamine tetraacetic acid (EDTA), gluconic acid, nitrotriacetic acid (NTA), hydroxyethyl ethylenediamine triacetic acid (HEDTA), and derivatives thereof can be mentioned.

The method of bringing the solution into contact with the conductive layer (a) is not limited. As a method of bringing the solution into contact with the conductive layer (a), for example, a method of applying the solution to the conductive layer (a) is mentioned. Examples of the coating method include an inkjet method, a spray method, a roll coating method, a bar coating method, a curtain coating method, and a die coating method (i.e., a slit coating method).

The method for producing a resin pattern preferably further includes a step of drying the solution adhering to the conductive layer (a). The drying temperature is preferably 25℃to 200℃and more preferably 25℃to 100 ℃.

The method for producing a resin pattern may further include a step of drying the solution adhering to the conductive layer (a) and a step of exposing the dried product of the solution to light. The preferred drying temperatures are as described above. The exposure is preferably 1mJ/cm ² ～1000mJ/cm ² More preferably 20mJ/cm ² ～750mJ/cm ² 。

The method for producing a resin pattern may further include a step of drying the solution adhering to the conductive layer (a), a step of exposing the dried product of the solution, and a step of heating the dried product of the solution. The preferred drying temperatures are as described above. The preferred exposure amounts are as described above. The heating temperature is preferably 30 to 200 ℃, more preferably 40 to 180 ℃. The heating time is preferably 0.1 to 3 hours, more preferably 0.1 to 1 hour.

In the surface modification step, at least a part of the components of the solution may form a layer or region significantly different from the conductive layer (a). In the surface modification step, at least a part of the components of the solution may form a layer or region integrated with the conductive layer (a). The two modes can be compatible. For example, in the surface modification step, a part of the components of the solution may be formed into a layer significantly different from the conductive layer (a), and a part of the components of the solution may be formed into a layer integrated with the conductive layer (a). In each of the above embodiments, at least a part of the components of the solution may permeate into the conductive layer (a). The above embodiments may be adopted within a range not departing from the gist of the present invention. The layer or region derived from the component of the solution is regarded as a part of the conductive layer in the step of forming the photosensitive resin layer described later.

[ step of Forming photosensitive resin layer ]

In the photosensitive resin layer forming step, a photosensitive resin layer is formed on the 2 nd surface of the conductive layer. The photosensitive resin layer has a 3 rd surface facing the conductive layer and a 4 th surface opposite to the 3 rd surface.

The surface free energy gamma s1 of the 2 nd surface of the conductive layer and the surface free energy gamma r of the 3 rd surface of the photosensitive resin layer satisfy the relation of |gammas 1-gammar| less than or equal to 12. The value of |γs1 to γr| is preferably 10 or less, more preferably 6 or less, and further preferably 4 or less. Further, the value of |γs1 to γr| is preferably 3 or less, more preferably 2.8 or less, and further preferably 2.5 or less. The lower limit of |γs1 to γr| is not limited from the viewpoint of adhesion between the conductive layer and the photosensitive resin layer. The value of |γs1 to γr| may be 0 or more.

In the present invention, the surface free energy of the photosensitive resin layer is calculated by a method based on the above-described calculation method of the surface free energy of the conductive layer. The following method is used for calculating the free energy of the surface of the photosensitive resin layer according to the method for forming the photosensitive resin layer.

(1) In the method for forming the photosensitive resin layer using the transfer material, the surface free energy of the photosensitive resin layer is calculated using a predetermined photosensitive resin layer disposed on the conductive layer. That is, in the method of forming the photosensitive resin layer using the transfer material, the surface free energy of the photosensitive resin layer is calculated before the photosensitive resin layer of the transfer material is adhered to the conductive layer. When the surface to be measured of the photosensitive resin layer is covered with another layer such as a protective film in the transfer material, the other layer is peeled off to calculate the surface free energy of the surface to be measured of the photosensitive resin layer.

(2) In the method of forming a photosensitive resin layer using a coating method, the surface free energy of the photosensitive resin layer is calculated using a photosensitive resin layer formed by coating a composition for forming a photosensitive resin layer onto a substrate having a low surface free energy (for example, cerapeel PJ271, TORAY INDUSTRIES, INC.). The specific steps are as follows. After forming the photosensitive resin layer on the substrate having a low surface free energy, the substrate is peeled from the photosensitive resin layer. The component of the substrate having a low surface free energy is selected from components which do not migrate into the photosensitive resin layer so as not to be corroded by the solvent contained in the composition for forming a photosensitive resin layer, and the component of the substrate is prevented from affecting the surface tension of the photosensitive resin layer. The surface of the photosensitive resin layer exposed by peeling the substrate was regarded as the 4 th surface of the photosensitive resin layer, and the surface free energy γr was calculated by the method described above.

The method for adjusting the surface free energy of the photosensitive resin layer is not limited. The surface free energy of the photosensitive resin layer can be adjusted according to the composition of the photosensitive resin layer.

Examples of the photosensitive resin layer include a positive photosensitive resin layer and a negative photosensitive resin layer.

From the viewpoint of resolution, the photosensitive resin layer is preferably a positive photosensitive resin layer. The photosensitive resin layer may be a positive photosensitive resin layer containing a polymer containing a structural unit having an acid group protected by an acid-decomposable group and a photoacid generator. The photosensitive resin layer may be a chemically amplified positive photosensitive resin layer containing a polymer containing a structural unit having an acid group protected by an acid-decomposable group and a photoacid generator. The photosensitive resin layer may be a positive photosensitive resin layer containing a naphthoquinone diazide compound and a phenol novolac resin as a photoreaction initiator.

The photosensitive resin layer is preferably a negative photosensitive resin layer from the viewpoints of strength, heat resistance and chemical resistance of the resin pattern. From the viewpoint of patterning, the negative photosensitive resin layer preferably contains a polymer having an acid group, a polymerizable compound, and a photopolymerization initiator. Examples of the negative photosensitive resin layer include a photosensitive resin layer described in japanese patent application laid-open No. 2016-224162.

(resin whose polarity is changed by acid)

The photosensitive resin layer (preferably, a positive photosensitive resin layer) preferably contains a resin whose polarity is changed by an acid.

Examples of the resin whose polarity is changed by the action of an acid include polymers containing a structural unit having an acid group protected by an acid-decomposable group. Hereinafter, the "structural unit having an acid group protected by an acid-decomposable group" may be referred to as "structural unit a". Hereinafter, the "polymer having a structural unit having an acid group protected by an acid-decomposable group" may be referred to as "polymer X1".

The polymer X1 is preferably a polyaddition type polymer, more preferably a polymer containing structural units derived from (meth) acrylic acid or (meth) acrylic esters.

The acid group protected by the acid-decomposable group is converted to an acid group by deprotection reaction under the action of a catalytic amount of an acidic substance (e.g., an acid) generated by exposure. The acid group is generated in the polymer X1 by the reaction as described above, and thus the solubility of the photosensitive resin layer in the developer increases.

The kind of the acid group is not limited. The acid group is preferably a carboxyl group or a phenolic hydroxyl group.

Examples of the acid-decomposable group include a group which is relatively easily decomposed by an acid and a group which is relatively hardly decomposed by an acid. Examples of the group which is relatively easily decomposed by an acid include acetal-type protecting groups (for example, 1-alkoxyalkyl groups, tetrahydropyranyl groups, and tetrahydrofuranyl groups). Examples of the group which is relatively hardly decomposed by an acid include a tertiary alkyl group (e.g., a tertiary butyl group) and a tertiary alkoxycarbonyl group (e.g., a tertiary butoxycarbonyl group). The acid-decomposable group is preferably an acetal-type protecting group.

From the viewpoint of suppressing variation in line width of the resin pattern, the molecular weight of the acid-decomposable group is preferably 300 or less.

From the viewpoints of sensitivity and resolution, the structural unit a is preferably at least one structural unit selected from the structural units represented by the following formula A1, the structural units represented by the following formula A2, and the structural units represented by the following formula A3, and more preferably the structural units represented by the following formula A3. The structural unit represented by the following formula A3 is a structural unit having a carboxyl group protected by an acetal acid-decomposable group.

[ chemical formula 1]

In the formula A1, R ¹¹ R is R ¹² Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ¹¹ R is R ¹² At least one of which is alkyl or aryl, R ¹³ Represents alkyl or aryl, R ¹¹ Or R is ¹² And R is R ¹³ Can be linked to each other to form a cyclic ether, R ¹⁴ Represents a hydrogen atom or a methyl group, X ¹ Represents a single bond or a divalent linking group, R ¹⁵ Represents a substituent, and n represents an integer of 0 to 4.

In the formula A2, R ²¹ R is R ²² Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ²¹ R is R ²² At least one of which is alkyl or aryl, R ²³ Represents alkyl or aryl, R ²¹ Or R is ²² And R is R ²³ Can be linked to each other to form a cyclic ether, R ²⁴ Each independently represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.

In the formula A3, R ³¹ R is R ³² Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ³¹ R is R ³² At least one of which is alkyl or aryl, R ³³ Represents alkyl or aryl, R ³¹ Or R is ³² And R is R ³³ Can be linked to each other to form a cyclic ether, R ³⁴ Represents a hydrogen atom or a methyl group, X ⁰ Represents a single bond or arylene.

In the formula A3, R is ³¹ R is R ³² The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms.

In the formula A3, R is ³¹ R is R ³² The aryl group represented is preferably phenyl.

In the formula A3, R ³¹ R is R ³² Each independently is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula A3, R ³³ Preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atomsIs a hydrocarbon group.

In the formula A3, R is ³¹ ～R ³³ The alkyl group and the aryl group may have a substituent.

In the formula A3, R ³¹ Or R is ³² And R is R ³³ Preferably linked to each other to form a cyclic ether. The number of ring members of the cyclic ether is preferably 5 or 6, more preferably 5.

In the formula A3, X ⁰ Preferably a single bond. From X ⁰ The arylene group represented may have a substituent.

In the formula A3, R ³⁴ Preferably a hydrogen atom. If R is ³⁴ Is a hydrogen atom, the glass transition temperature (Tg) of the polymer X1 tends to decrease.

R in formula A3 ³⁴ The content of the structural unit which is a hydrogen atom is preferably 20 mass% or more with respect to the total mass of the structural unit a contained in the polymer X1. R in formula A3 ³⁴ The content of the structural unit which is a hydrogen atom in the structural unit A is confirmed by the intensity ratio of the peak intensities according to ¹³ C-Nuclear magnetic resonance Spectrometry (NMR) determination is calculated by conventional methods.

As a preferable mode of the formulas A1 to A3, reference is made to paragraphs 0044 to 0058 of International publication No. 2018/179640.

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

The polymer X1 may contain one or more than two structural units A.

The content of the structural unit a is preferably 10 to 70% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 40% by mass relative to the total mass of the polymer X1. By the content of the structural unit a being within the above range, the resolution is further improved. In the case where the polymer X1 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 structural unit A passes through the peak intensity Is confirmed according to the intensity ratio of the peak intensities ¹³ The C-NMR measurement was calculated by a conventional method.

The polymer X1 may further contain a structural unit having an acid group (hereinafter, sometimes referred to as "structural unit B"). The structural unit B is a structural unit having an acid group not protected by an acid-decomposable group (i.e., an acid group having no protecting group). By containing the structural unit B in the polymer X1, the sensitivity at the time of pattern formation becomes good. The structural unit B makes the polymer X1 easily soluble in an alkaline developer, and therefore can shorten the development time.

The acid group in the structural unit B represents a proton dissociable group having 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. The pKa of the acid group is preferably-5 or more. Examples of the acid group include a carboxyl group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group. The acid group is preferably a carboxyl group or a phenolic hydroxyl group, more preferably a carboxyl group.

The polymer X1 may contain one or two or more structural units B.

The content of the structural unit B is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and even more preferably 0.1 to 5% by mass relative to the total mass of the polymer X1. By the content of the structural unit B being within the above range, resolution becomes better. In the case where the polymer X1 contains two or more structural units B, the content of the structural units B represents the total content of the two or more structural units B. The content of the structural unit B was confirmed by the intensity ratio of the peak intensities according to ¹³ The C-NMR measurement was calculated by a conventional method.

The polymer X1 may further contain other structural units (hereinafter, sometimes referred to as "structural unit C"). By adjusting at least one of the type and the content of the structural unit C, each characteristic of the polymer X1 can be adjusted. For example, the structural unit C can easily adjust the glass transition temperature, acid value, and hydrophilicity/hydrophobicity of the polymer X1.

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

From the viewpoint of adhesion between the conductive layer and the photosensitive resin layer, the monomer forming the structural unit C is preferably an alkyl (meth) acrylate, and more preferably an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

Examples of the structural unit C include structural units derived from styrene, α -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 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-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, or ethylene glycol monoacetoacetate mono (meth) acrylate. The structural unit C may be a structural unit derived from a compound described in paragraphs 0021 to 0024 of Japanese unexamined patent publication No. 2004-264623.

From the viewpoint of resolution, the structural unit C is preferably a structural unit having a basic group. Examples of the basic group include a group having a nitrogen atom. Examples of the group having a nitrogen atom include an aliphatic amino group, an aromatic amino group, and a nitrogen-containing heteroaromatic group. 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. From the viewpoint of resolution, the aliphatic amino group is preferably a secondary amino group or a tertiary amino group.

As the monomer forming the structural unit having a basic group, examples thereof include 1,2, 6-pentamethyl-4-piperidinyl methacrylate, 2- (dimethylamino) ethyl methacrylate, 2, 6-tetramethyl-4-piperidinyl acrylate, 2, 6-tetramethyl-4-piperidinyl methacrylate, 2, 6-tetramethyl-4-piperidinyl acrylate, and 2- (diethylamino) ethyl methacrylate, 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate N- (3-diethylamino) propyl methacrylate, N- (3-diethylamino) propyl acrylate, 2- (diisopropylamino) ethyl methacrylate, 2-morpholinoethyl acrylate, N- [3- (dimethylamino) propyl ] acrylamide, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole and 1-vinyl-1, 2, 4-triazole. Among the above, 1,2, 6-pentamethyl-4-piperidinyl methacrylate is preferable.

From the viewpoint of improving electrical characteristics, the structural unit C is preferably a structural unit having an aromatic ring or a structural unit having an aliphatic ring skeleton. Examples of the monomer forming the structural unit include styrene, α -methylstyrene, dicyclopentanyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate. Among the above, cyclohexyl (meth) acrylate is preferable.

The polymer X1 may contain one or more than two structural units C.

The content of the structural unit C is preferably 90 mass% or less, more preferably 85 mass% or less, and further preferably 80 mass% or less, relative to the total mass of the polymer X1. The content of the structural unit C is preferably 10 mass% or more, more preferably 20 mass% or more, relative to the total mass of the polymer X1. The content of the structural unit C is within the above range, and the resolution and adhesion between the conductive layer and the photosensitive resin layer are obtainedThe sex is further improved. In the case where the polymer X1 has two or more structural units C, the content of the structural units C represents the total content of the two or more structural units C. The content of the structural unit C was confirmed by the intensity ratio of the peak intensities according to ¹³ The C-NMR measurement was calculated by a conventional method.

Preferred examples of the polymer X1 are shown below. However, the polymer X1 is not limited to the following examples. The ratio of each structural unit and the weight average molecular weight in the polymer X1 shown below can be appropriately selected to obtain preferable physical properties.

[ chemical formula 2]

The glass transition temperature (Tg) of the polymer X1 is preferably 90℃or lower, more preferably 20℃to 60℃and particularly preferably 30℃to 50 ℃. The glass transition temperature of the polymer X1 is in the above range, whereby the transferability of the photosensitive resin layer is improved.

As a method for adjusting the glass transition temperature (Tg) of the polymer X1, for example, a method using FOX formula is mentioned. For example, the FOX formula may adjust the glass transition temperature of the target polymer X1 according to the glass transition temperature of the homopolymer of each structural unit contained in the target polymer X1 and the mass fraction of each structural unit. Hereinafter, the FOX formula will be described by taking a copolymer containing the 1 st structural unit and the 2 nd structural unit as an example. When the glass transition temperature of the homopolymer of the 1 st structural unit is Tg1, the mass fraction of the 1 st structural unit in the copolymer is W1, the glass transition temperature of the homopolymer of the 2 nd structural unit is Tg2, and the mass fraction of the 2 nd structural unit in the copolymer is W2, the glass transition temperature Tg0 (unit: K) of the copolymer containing the 1 st structural unit and the 2 nd structural unit is estimated from the following formula.

FOX formula: 1/Tg 0= (W1/Tg 1) + (W2/Tg 2)

The glass transition temperature (Tg) of the polymer X1 can be adjusted according to the weight average molecular weight of the polymer.

From the viewpoint of resolution, the acid value of the polymer X1 is preferably 0mgKOH/g to 50mgKOH/g, more preferably 0mgKOH/g to 20mgKOH/g, still more preferably 0mgKOH/g to 10mgKOH/g.

The weight average molecular weight (Mw) of the polymer X1 is preferably 60,000 or less. The weight average molecular weight of the polymer X1 is represented by a polystyrene-equivalent weight average molecular weight. The transferability of the photosensitive resin layer at low temperature (for example, 130 ℃ or lower) is improved by the weight average molecular weight of the polymer X1 being 60,000 or lower. The weight average molecular weight of the polymer X1 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 (i.e., dispersity) of the polymer X1 is preferably 1.0 to 5.0, more preferably 1.05 to 3.5. Dispersity refers to the ratio of weight average molecular weight to number average molecular weight (i.e., weight average molecular weight/number average molecular weight).

The weight average molecular weight of the polymer X1 was determined by GPC (gel permeation chromatography). Specific examples of the method for measuring the weight average molecular weight of the polymer X1 are shown below.

(1) Measurement device: HLC (registered trademark) -8220GPC (TOSOH CORPORATION)

(2) And (3) pipe column: a column was constructed by connecting in series one TSKgel (registered trademark) Super HZM-M (4.6 mmID. Times.15 cm, TOSOH CORPORATION), one Super HZ4000 (4.6 mmID. Times.15 cm, TOSOH CORPORATION), one Super HZ3000 (4.6 mmID. Times.15 cm, TOSOH CORPORATION) and one Super HZ2000 (4.6 mmID. Times.15 cm, TOSOH CORPORATION)

(3) Eluent: THF (tetrahydrofuran)

(4) Sample concentration: 0.2 mass%

(5) Flow rate: 0.35 mL/min

(6) Sample injection amount: 10 mu L

(7) Measuring temperature: 40 DEG C

(8) A detector: differential Refractive Index (RI) detector

(9) Calibration curve: using TOSOH CORPORATION "standard sample TSK standard, polystyrene": calibration curves made for any of the seven samples "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500", and "A-1000"

The photosensitive resin layer may contain one or two or more kinds of polymers X1.

From the viewpoint of high resolution, the content of the polymer X1 is preferably 50 to 99.9 mass%, more preferably 70 to 98 mass%, relative to the total mass of the photosensitive resin layer.

The method for producing the polymer X1 is not limited. For example, the polymer X1 is produced by polymerizing a monomer for forming the structural unit a, a monomer for forming the structural unit B, and a monomer for forming the structural unit C, which are polymerized as needed, in an organic solvent using a polymerization initiator. The polymer X1 can also be produced by a polymer reaction.

(Polymer containing no structural unit having an acid group protected with an acid-decomposable group)

In addition to the polymer X1, the photosensitive resin layer (preferably, a positive photosensitive resin layer) may contain a polymer that does not contain a structural unit having an acid group protected by an acid-decomposable group. Hereinafter, the "polymer having no structural unit having an acid group protected by an acid-decomposable group" may be referred to as "polymer X2".

Examples of the polymer X2 include polyhydroxystyrene.

Examples of commercial products of polyhydroxystyrene include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P and SMA3840F manufactured by Sartomer Company inc.

Examples of commercial products of polyhydroxystyrene include TOAGOSEI CO., LTD. ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080.

Examples of commercial products of polyhydroxystyrene include Joncryl 690, joncryl 678, joncryl 67, and Joncryl 586 manufactured by BASF corporation.

The photosensitive resin layer may contain one or two or more polymers X2.

When the photosensitive resin layer contains the polymer X2, the content of the polymer X2 is preferably 50 mass% or less, more preferably 30 mass% or less, and still more preferably 20 mass% or less, relative to the total mass of the polymer components.

In the present invention, the "polymer component" is a generic term for all polymers contained in the photosensitive resin layer. For example, when the photosensitive resin layer contains the polymer X1 and the polymer X2, the polymer X1 and the polymer X2 are collectively referred to as "polymer components". The compound corresponding to the crosslinking agent, the dispersant and the surfactant does not contain a polymer component even if it is a polymer compound.

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

(photoacid generator)

The photosensitive resin layer (preferably, a positive photosensitive resin layer) preferably contains a photoacid generator. The photosensitive resin layer (preferably, a positive photosensitive resin layer) more preferably contains a resin whose polarity is changed by an acid and a photoacid generator.

Photoacid generators are compounds that generate acid upon receiving activating light (e.g., ultraviolet, extreme ultraviolet, X-rays, and electron beams).

The photoacid generator is preferably a compound that generates an acid by sensing an activating light having a wavelength of 300nm or more (preferably, a wavelength of 300nm to 450 nm). The photoacid generator that does not directly induce an activating light having a wavelength of 300nm or more is preferably used in combination with a sensitizer as long as it is a compound that generates an acid by inducing an activating light having a wavelength of 300nm or more together with the sensitizer.

The photoacid generator is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and still more preferably a photoacid generator that generates an acid having a pKa of 2 or less. The lower limit of the pKa of the acid derived from the photoacid generator is not limited. The pKa of the acid derived from the photoacid generator is preferably-10.0 or more.

Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.

Examples of the ionic photoacid generator include onium salt compounds. Examples of the onium salt compound include a diaryliodonium salt compound, a triarylsulfonium salt compound, and a quaternary ammonium salt compound. The ionic photoacid generator is preferably an onium salt compound, and more preferably at least one compound selected from a triarylsulfonium salt compound and a diaryliodonium salt compound.

Examples of preferable ionic photoacid generators include those described in paragraphs 0114 to 0133 of JP-A2014-85643.

Examples of the nonionic photoacid generator include a trichloromethyl s-triazine compound, a diazomethane compound, an imide sulfonate compound, and an oxime sulfonate compound. The nonionic photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion between the conductive layer and the photosensitive resin layer.

Specific examples of the trichloromethyl s-triazine compound, the diazomethane compound and the imide sulfonate compound are described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494.

Examples of preferable oxime sulfonate compounds include those described in paragraphs 0084 to 0088 of International publication No. 2018/179640.

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

Examples of the photoacid generator include photoacid generators having the following structures.

[ chemical formula 3]

The photosensitive resin layer may contain one or two or more photoacid generators.

From the viewpoints of sensitivity and resolution, the content of the photoacid generator is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, relative to the total mass of the photosensitive resin layer.

(resin having phenolic hydroxyl group)

The photosensitive resin layer (preferably, a positive photosensitive resin layer) preferably contains a resin having a phenolic hydroxyl group.

The phenolic hydroxyl groups may be disposed in the main chain or side chain of the resin.

Examples of the resin having a phenolic hydroxyl group include novolak resins. For example, a novolak resin is obtained by condensing a phenol compound and an aldehyde compound in the presence of an acid catalyst. Examples of the phenol compound include o-cresol, m-cresol, p-cresol, 2, 5-xylenol, 3, 4-xylenol, 2,3, 5-trimethylphenol, 2-t-butyl-5-methylphenol, and t-butylhydroquinone. Examples of the aldehyde compound include aliphatic aldehydes (for example, formaldehyde, acetaldehyde, and glyoxal) and aromatic aldehydes (for example, benzaldehyde and salicylaldehyde). Examples of the acid catalyst include inorganic acids (e.g., hydrochloric acid, sulfuric acid, and phosphoric acid), organic acids (e.g., oxalic acid, acetic acid, and p-toluenesulfonic acid), and divalent metal salts (e.g., zinc acetate). The condensation reaction may be carried out according to a known method. For example, the condensation reaction is carried out at a temperature in the range of 60 to 120℃for 2 to 30 hours. The condensation reaction may be carried out in a suitable solvent.

The resin having a phenolic hydroxyl group is preferably alkali-soluble. In the present invention, "alkali solubility" means a property that the solubility in 100g of a 1 mass% aqueous solution of sodium carbonate is 0.1g or more at a liquid temperature of 22 ℃.

The photosensitive resin layer may contain one or two or more resins having phenolic hydroxyl groups.

From the viewpoints of resolution and developability, the content of the resin having a phenolic hydroxyl group is preferably 10 to 90% by mass, more preferably 20 to 90% by mass, and still more preferably 30 to 90% by mass relative to the total mass of the photosensitive resin layer.

(quinone diazide derivative)

The photosensitive resin layer (preferably, a positive photosensitive resin layer) preferably contains a quinone diazide derivative. The photosensitive resin layer (preferably, a positive photosensitive resin layer) more preferably contains a resin having a phenolic hydroxyl group and a quinone diazide derivative. The quinone diazide derivative can contribute to heat resistance and dimensional stability of the photosensitive resin layer.

Examples of the quinone diazide derivative include sulfonic acid esters of quinone diazide derivatives and sulfonic acid halides of quinone diazide derivatives.

Examples of the sulfonic acid ester of the quinone diazide derivative include 1, 2-benzoquinone diazide-4-sulfonic acid ester, 1, 2-naphthoquinone diazide-5-sulfonic acid ester, 1, 2-naphthoquinone diazide-6-sulfonic acid ester, 2, 1-naphthoquinone diazide-4-sulfonic acid ester, 2, 1-naphthoquinone diazide-5-sulfonic acid ester and 2, 1-naphthoquinone diazide-6-sulfonic acid ester.

Examples of the sulfonic acid halide of the quinone diazide derivative include 1, 2-benzoquinone diazide-4-sulfonyl chloride, 1, 2-naphthoquinone diazide-5-sulfonyl chloride, 1, 2-naphthoquinone diazide-6-sulfonyl chloride, 2, 1-naphthoquinone diazide-4-sulfonyl chloride, 2, 1-naphthoquinone diazide-5-sulfonyl chloride, and 2, 1-naphthoquinone diazide-6-sulfonyl chloride.

The method for producing the quinone diazide derivative is not limited. For example, the quinone diazide derivative is produced by subjecting a compound having a phenolic hydroxyl group and a quinone diazide sulfonyl halide to a condensation reaction in the presence of a dehydrohalogenating agent.

The photosensitive resin layer may contain one or two or more kinds of quinone diazide derivatives.

From the viewpoints of resolution and developability, the content of the quinone diazide derivative is preferably 0.1 to 30 mass%, more preferably 0.1 to 25 mass%, and even more preferably 0.5 to 20 mass% relative to the total mass of the photosensitive resin layer.

(alkaline Compound)

The photosensitive resin layer (preferably, a positive photosensitive resin layer) may contain an alkaline compound.

Examples of the basic compound include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples of the basic compound include compounds described in paragraphs 0204 to 0207 of Japanese patent application laid-open No. 2011-221494. The contents of the above documents are incorporated by reference into the present specification.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, and dicyclohexylamine.

Examples of the aromatic amine include aniline, benzylamine, N-dimethylaniline and diphenylamine.

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4, 5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1, 5-diazabicyclo [4.3.0] -5-nonene, and 1, 8-diazabicyclo [5.3.0] -7-undecene.

Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

Examples of the quaternary ammonium salt of carboxylic acid include tetramethyl ammonium acetate, tetramethyl ammonium benzoate, tetra-n-butyl ammonium acetate and tetra-n-butyl ammonium benzoate.

The alkaline compound is preferably a benzotriazole compound from the viewpoints of rust resistance of the conductive layer and linearity of the conductive pattern.

The benzotriazole compound is a compound having a benzotriazole skeleton. The benzotriazole compound may be selected from known benzotriazole compounds. Examples of the benzotriazole compound include 1,2, 3-benzotriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] benzotriazole, 5-carboxybenzotriazole, 1- (hydroxymethyl) -1H-benzol, 1-acetyl-1H-benzol, 1-aminobenzol, 9- (1H-benzotriazol-1-ylmethyl) -9H-carbazole, 1-chloro-1H-benzol-triazole, 1- (2-pyridyl) benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-ethylbenzotriazole, 1- (1 ' -hydroxyethyl) benzotriazole, 1- (2 ' -hydroxyethyl) benzotriazole, 1-propylbenzotriazole, 1- (1 ' -hydroxypropyl) benzotriazole, 1- (2 ' -hydroxypropyl) benzotriazole, 1- (3 ' -hydroxypropyl) benzotriazole, 4-hydroxy-1H-benzol-benzotriazole, 5-methyl-1H-benzotriazol, methylbenzotriazole-5-benzotriazol-carboxylate, benzotriazole-5-ethyl-benzotriazol-5-carboxylate, and 1-methyl-1-benzotriazol-5-carboxylate, and 1-ethyl-benzotriazol-5-carboxylate 2-methyl-2H-benzotriazole and 2-ethyl-2H-benzotriazole.

The photosensitive resin layer may contain one or two or more kinds of basic compounds.

The content of the alkaline compound is preferably 0.001 to 5 mass%, more preferably 0.005 to 3 mass%, based on the total mass of the photosensitive resin layer.

The form of the basic compound is described in International publication No. 2018/179640. The contents of the above documents are incorporated by reference into the present specification.

(alkoxysilane compound)

The photosensitive resin layer (preferably, a positive photosensitive resin layer) may contain an alkoxysilane compound.

Examples of alkoxysilane compounds include gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trialkoxysilane, gamma-glycidoxypropyl alkyl dialkoxysilane, gamma-methacryloxypropyl trialkoxysilane, gamma-methacryloxypropyl alkyl dialkoxysilane, gamma-chloropropyl trialkoxysilane, gamma-mercaptopropyl trialkoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl trialkoxysilane and vinyl trialkoxysilane.

The alkoxysilane compound is preferably a trialkoxysilane compound, more preferably γ -glycidoxypropyl trialkoxysilane or γ -methacryloxypropyl trialkoxysilane, further preferably γ -glycidoxypropyl trialkoxysilane, and particularly preferably 3-glycidoxypropyl trimethoxysilane.

The photosensitive resin layer may contain one or two or more alkoxysilane compounds.

From the viewpoints of adhesion between the conductive layer and the photosensitive resin layer and etching resistance, the content of the alkoxysilane compound is preferably 0.1 to 50 mass%, more preferably 0.5 to 40 mass%, and even more preferably 1.0 to 30 mass% relative to the total mass of the photosensitive resin layer.

The alkoxysilane compound is described in International publication No. 2018/179640. The contents of the above documents are incorporated by reference into the present specification.

(alkali-soluble resin)

The photosensitive resin layer (preferably, a negative photosensitive resin layer) preferably contains an alkali-soluble resin.

Examples of the alkali-soluble resin include known alkali-soluble resins used for resists.

The alkali-soluble resin is preferably a binder polymer.

The alkali-soluble resin is preferably an alkali-soluble resin having an acid group.

The alkali-soluble resin is preferably a compound collectively referred to as "polymer a" in the following description.

The acid value of the polymer a is preferably 220mgKOH/g or less, more preferably less than 200mgKOH/g, and even more preferably less than 190mgKOH/g, from the viewpoint of improving resolution by suppressing swelling of the photosensitive resin layer by the developer. The acid value of the polymer A is preferably 60mgKOH/g or more, more preferably 120mgKOH/g or more, still more preferably 150mgKOH/g or more, particularly preferably 170mgKOH/g or more, from the viewpoint of further excellent developability. For example, the acid value of the polymer a is adjusted according to the kind of the structural unit constituting the polymer a and the content of the structural unit containing an acid group.

The weight average molecular weight of polymer a is preferably 5,000 ～ 500,000. From the viewpoint of improving resolution and developability, the weight average molecular weight of the polymer a is preferably adjusted to 500,000 or less. The weight average molecular weight of the polymer a is preferably 100,000 or less, more preferably 60,000 or less, and further preferably 50,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film (for example, edge fusion property and chipping property), the weight average molecular weight of the polymer a is preferably adjusted to 5,000 or more. The weight average molecular weight of the polymer a is preferably 10,000 or more, more preferably 20,000 or more, and still more preferably 30,000 or more. The edge-fusing property is a degree to which the photosensitive resin layer easily protrudes from the end surface of the roll when an article (e.g., a transfer material) including the photosensitive resin layer is wound into a roll. The chipability means the degree to which the chip is easily scattered when the unexposed film is cut by a cutter. If the chips adhere to the surface of the photosensitive resin layer, the chips may be transferred to the mask in a subsequent process, and the product may be rejected. The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, particularly preferably 1.0 to 3.0.

From the viewpoint of suppressing deterioration of the thickness and resolution of the line width at the time of focus position deviation at the time of exposure, polymer a preferably contains a structural unit having an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content of the structural unit having an aromatic hydrocarbon group in the polymer a is preferably 20 mass% or more, more preferably 30 mass% or more, still more preferably 40 mass% or more, particularly preferably 45 mass% or more, and most preferably 50 mass% or more, based on the total mass of all the structural units. In the polymer a, the content of the structural unit having an aromatic hydrocarbon group is preferably 95 mass% or less, more preferably 85 mass% or less, based on the total mass of all the structural units. When the photosensitive resin layer contains two or more polymers a, the content of the structural units having an aromatic hydrocarbon group is determined as a weight average value.

Examples of the monomer forming the structural unit having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, t-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer). Monomers having aralkyl groups or styrene are preferred. In the case where the structural unit having an aromatic hydrocarbon group in the polymer a is a structural unit derived from styrene, the content of the structural unit derived from styrene in the polymer a is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, still more preferably 30 to 40% by mass, and particularly preferably 30 to 35% by mass, based on the total mass of all the structural units.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group. Preferably a substituted or unsubstituted benzyl group.

Examples of the monomer having a phenylalkyl group include phenethyl (meth) acrylate.

Examples of the monomer having a benzyl group include (meth) acrylic acid esters having a benzyl group (e.g., benzyl (meth) acrylate and chlorobenzyl (meth) acrylate) and vinyl monomers having a benzyl group (e.g., vinylbenzyl chloride and vinylbenzyl alcohol). Benzyl (meth) acrylate is preferred. In the case where the structural unit having an aromatic hydrocarbon group in the polymer a is a structural unit derived from benzyl (meth) acrylate, the content of the structural unit derived from benzyl (meth) acrylate is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, still more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, based on the total mass of all the structural units.

The polymer a containing a structural unit having an aromatic hydrocarbon group is preferably a polymer obtained by polymerizing a monomer having an aromatic hydrocarbon group and at least one monomer selected from the 1 st monomer and the 2 nd monomer.

The polymer a containing no structural unit having an aromatic hydrocarbon group is preferably a polymer obtained by polymerizing the 1 st monomer, more preferably a polymer obtained by copolymerizing the 1 st monomer and the 2 nd monomer.

The 1 st monomer is a monomer having a carboxyl group in the molecule. Examples of the 1 st monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. (meth) acrylic acid is preferred.

In the polymer a, the content of the structural unit derived from the 1 st monomer is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, based on the total mass of all the structural units.

The copolymerization ratio of the 1 st monomer is preferably 10 to 50% by mass based on the total mass of all the structural units. From the viewpoint of exhibiting good developability and controlling edge fusion, the copolymerization ratio of the 1 st monomer is preferably 10 mass% or more. The copolymerization ratio of the 1 st monomer is preferably 15 mass% or more, more preferably 20 mass% or more, based on the total mass of all the structural units. From the viewpoints of high resolution of the resin pattern, bottom shape of the resin pattern, and chemical resistance of the resin pattern, the copolymerization ratio of the 1 st monomer is preferably 50 mass% or less. The copolymerization ratio of the 1 st monomer is preferably 35 mass% or less, more preferably 30 mass% or less, and further preferably 27 mass% or less based on the total mass of all the structural units.

The 2 nd monomer is a non-acidic monomer having at least one polymerizable unsaturated group. Examples of the 2 nd monomer include (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; esters of vinyl alcohol such as vinyl acetate; (meth) acrylonitrile. Methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl (meth) acrylate are preferable, and methyl (meth) acrylate is more preferable.

In the polymer a, the content of the structural unit derived from the 2 nd monomer is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 45% by mass, based on the total mass of all the structural units.

From the viewpoint of suppressing deterioration of the thickness and resolution of the line width at the time of focus position deviation at the time of exposure, the polymer a preferably contains at least one structural unit selected from structural units having an aralkyl group and structural units derived from styrene. Preferable examples of the polymer a containing the structural unit include a copolymer of methacrylic acid, benzyl methacrylate and styrene, and a copolymer of methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene.

The polymer a preferably contains 25 to 40 mass% of a structural unit having an aromatic hydrocarbon group, 20 to 35 mass% of a structural unit derived from the 1 st monomer, and 30 to 45 mass% of a structural unit derived from the 2 nd monomer.

The polymer a preferably contains 70 to 90 mass% of a structural unit having an aromatic hydrocarbon group and 10 to 25 mass% of a structural unit derived from the 1 st monomer.

The side chains of the polymer a may have a linear structure, a branched structure, or an alicyclic structure. For example, a branched structure or an alicyclic structure is introduced into the side chain of the polymer a by using a monomer having a group having a branched structure in the side chain or a monomer having a group having an alicyclic structure in the side chain. The group having an alicyclic structure may be monocyclic or polycyclic.

Examples of the monomer having a group having a branched structure in a side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isopentyl (meth) acrylate, tert-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, and tert-octyl (meth) acrylate. Isopropyl (meth) acrylate, isobutyl (meth) acrylate or tert-butyl methacrylate is preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred.

Examples of the monomer having a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Examples of the monomer having an alicyclic structure in the side chain include (meth) acrylic esters having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. As the monomer having a group having an alicyclic structure in a side chain, examples thereof include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2) ester, (meth) acrylic acid-1-adamantyl ester, (meth) acrylic acid-2-adamantyl ester, (meth) acrylic acid-3-methyl-1-adamantyl ester, (meth) acrylic acid-3, 5-dimethyl-1-adamantyl ester, (meth) acrylic acid-3-ethyladamantanyl ester, (meth) acrylic acid-3-methyl-5-ethyl-1-adamantyl ester, (meth) acrylic acid-3, 5, 8-triethyl-1-adamantyl ester, (meth) acrylic acid-3, 5-dimethyl-8-ethyl-1-adamantyl ester, (meth) acrylic acid-2-methyl-2-adamantyl ester, (meth) acrylic acid-2-ethyl-2-adamantyl ester, (meth) acrylic acid-3-hydroxy-1-adamantyl ester, (meth) acrylic acid octahydro-4, 7-menthol inden-5-yl ester, (meth) acrylic acid-1-menthyl ester, and (meth) acrylic acid menthyl ester, 3-hydroxy-2, 6-trimethyl-bicyclo [3.1.1] heptyl (meth) acrylate, 3, 7-trimethyl-4-hydroxy-bicyclo [4.1.0] heptyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate. Preferably cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl (meth) acrylate or tricyclodecyl (meth) acrylate, more preferably cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate or tricyclodecyl (meth) acrylate.

The photosensitive resin layer may contain one or two or more kinds of polymers a.

The photosensitive resin layer may contain two kinds of polymers a containing a structural unit having an aromatic hydrocarbon group. The photosensitive resin layer may contain: a polymer A containing a structural unit having an aromatic hydrocarbon group and a polymer A not containing a structural unit having an aromatic hydrocarbon group. In the latter, the proportion of the polymer a containing a structural unit having an aromatic hydrocarbon group to be used is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the polymer a.

The glass transition temperature (Tg) of the polymer A is preferably 30℃or more and 135℃or less. When the glass transition temperature of the polymer A is 135 ℃ or lower, deterioration of line width roughness and resolution at the time of focus position deviation at the time of exposure can be suppressed. The glass transition temperature of the polymer A is preferably 130℃or lower, more preferably 120℃or lower, and further preferably 110℃or lower. When the glass transition temperature of the polymer A is 30℃or higher, the edge fusion resistance is improved. The glass transition temperature of the polymer A is preferably 40℃or higher, more preferably 50℃or higher, still more preferably 60℃or higher, and particularly preferably 70℃or higher.

The polymer a is preferably produced, for example, by adding an appropriate amount of a radical polymerization initiator (e.g., benzoyl peroxide and azoisobutyronitrile) to a solution obtained by diluting a monomer with a solvent (e.g., acetone, methyl ethyl ketone, and isopropyl alcohol) and stirring the mixture with heating. The polymer A may be produced by dropping a part of the mixture into the reaction solution. After the completion of the reaction, a solvent may be added to the reaction solution to adjust the concentration to a desired level. As the synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The photosensitive resin layer may contain one or two or more alkali-soluble resins.

The content of the alkali-soluble resin is preferably 10 to 90 mass%, more preferably 30 to 70 mass%, and even more preferably 40 to 60 mass% relative to the total mass of the photosensitive resin layer. For example, from the viewpoint of controlling the development time, the proportion of the alkali-soluble resin to the negative photosensitive resin layer is preferably 90 mass% or less. For example, from the viewpoint of improving the edge fusion resistance, the proportion of the alkali-soluble resin to the negative photosensitive resin layer is preferably 10 mass% or more.

The photosensitive resin layer may contain a resin other than the alkali-soluble resin. Examples of the resin other than the alkali-soluble resin include acrylic resins, styrene-acrylic copolymers (however, copolymers having a styrene content of 40 mass% or less), polyurethanes, polyvinyl alcohols, polyvinyl formals, polyamides, polyesters, epoxy resins, polyacetals, polyhydroxystyrenes, polyimides, polybenzoxazoles, polysiloxanes, polyethyleneimines, polyallylamines, and polyalkylene glycols.

(polymerizable Compound)

The photosensitive resin layer (preferably, a negative photosensitive resin layer) preferably contains a polymerizable compound. The photosensitive resin layer (preferably, a negative photosensitive resin layer) more preferably contains an alkali-soluble resin and a polymerizable compound.

The polymerizable compound may be selected from known polymerizable compounds. The polymerizable compound is preferably an ethylenically unsaturated compound. The ethylenically unsaturated compound is a compound having at least one ethylenically unsaturated group. The ethylenically unsaturated compound contributes to photosensitivity (i.e., photocurability) of the negative photosensitive resin layer and strength of the cured film.

The ethylenically unsaturated group is preferably a (meth) acryloyl group.

The ethylenically unsaturated compound is preferably a (meth) acrylate compound.

Examples of the ethylenically unsaturated compounds include caprolactone-modified (meth) acrylate compounds [ e.g., nippon Kayaku Co., ltd., KAYARAD (registered trademark) DPCA-20 and SHIN-NAKAMURA CHEMICAL CO ], LTD. A-9300-1CL ], alkylene oxide-modified (meth) acrylate compounds [ e.g., nippon Kayaku Co., ltd., KAYARAI) RP-1040, SHIN-NAKAMURA CHEMICAL CO, LTD. ATM-35E and A-9300, and DAICEL-ALLNEX LTD., EBECRYL (registered trademark) 135 ], ethoxylated glycerol triacrylates [ e.g., SHIN-NAKAMURA CHEMICAL CO, LTD. A-GLY-9E ], ARONIX (registered trademark) TO-2349 (AGOSEI CO., LTD.), ARONIX M-520 (TOOSEI CO., LTD.)), LTONIX-510 (LTEI) and SHUX (LTD) and LTD-56 CO., LTD-56, and LTD-56 CO, and LTD (registered trademark) and LTD-35 CO, LTD..

Examples of the ethylenically unsaturated compound include polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942.

Examples of the preferable ethylenically unsaturated compound include a compound having at least two ethylenically unsaturated groups.

Examples of the compound having two ethylenically unsaturated groups (hereinafter referred to as "2-functional ethylenically unsaturated compound") include tricyclodecane dimethanol diacrylate (A-DCP, SHIN-NAKAMURA CHEMICAL CO, LTD.), tricyclodecane dimethanol dimethacrylate (DCP, SHIN-NAKAMURA CHEMICAL CO, LTD.), 1, 9-nonanediol diacrylate (A-NOD-N, SHIN-NAKAMURA CHEMICAL CO, LTD.), and 1, 6-hexanediol dimethacrylate (HD-N, SHIN-NAKAMURA CHEMICAL CO, LTD.).

As the preferable 2-functional ethylenically unsaturated compound, for example, a 2-functional ethylenically unsaturated compound having a bisphenol structure can be mentioned.

Examples of the 2-functional ethylenically unsaturated compound having a bisphenol structure include those described in paragraphs 0072 to 0080 of JP-A2016-224162.

Examples of the 2-functional ethylenically unsaturated compound having a bisphenol structure include alkylene oxide-modified bisphenol A di (meth) acrylate.

Examples of the alkylene oxide-modified bisphenol a di (meth) acrylate include ethylene glycol dimethacrylate obtained by adding an average of 5 moles of ethylene oxide to each of both ends of bisphenol a, ethylene glycol dimethacrylate obtained by adding an average of 2 moles of ethylene oxide to each of both ends of bisphenol a, ethylene glycol dimethacrylate obtained by adding an average of 5 moles of ethylene oxide to each of both ends of bisphenol a, alkylene glycol dimethacrylate obtained by adding an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide to each of both ends of bisphenol a, and alkylene glycol dimethacrylate obtained by adding an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol a.

Specific examples of the alkylene oxide-modified bisphenol A di (meth) acrylate include 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane and 2, 2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane.

As a commercial product of alkylene oxide-modified bisphenol A di (meth) acrylate, BPE-500 (SHIN-NAKAMURA CHEMICAL CO, LTD.) is mentioned, for example.

Examples of the compound having at least three ethylenically unsaturated groups (hereinafter referred to as "ethylenically unsaturated compound having 3 or more functions") include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and glycerol tri (meth) acrylate. "(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.

The ethylenically unsaturated compound having 3 or more functions is preferably a tetramethyl acrylate obtained by adding an average of 9 moles of ethylene oxide to the terminal end of the hydroxyl group of pentaerythritol, a tetramethyl acrylate obtained by adding an average of 12 moles of ethylene oxide to the terminal end of the hydroxyl group of pentaerythritol, a tetramethyl acrylate obtained by adding an average of 15 moles of ethylene oxide to the terminal end of the hydroxyl group of pentaerythritol, a tetramethyl acrylate obtained by adding an average of 20 moles of ethylene oxide to the terminal end of the hydroxyl group of pentaerythritol, a tetramethyl acrylate obtained by adding an average of 28 moles of ethylene oxide to the terminal end of the hydroxyl group of pentaerythritol, or a tetramethyl acrylate obtained by adding an average of 35 moles of ethylene oxide to the terminal end of the hydroxyl group of pentaerythritol.

The molecular weight of the polymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and still more preferably 300 to 2,200. When the polymerizable compound has a molecular weight distribution, the weight average molecular weight (Mw) of the polymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and further preferably 300 to 2,200.

The photosensitive resin layer may contain one or two or more kinds of polymerizable compounds.

The content of the polymerizable compound is preferably 10 to 70 mass%, more preferably 20 to 60 mass%, and even more preferably 20 to 50 mass% based on the total mass of the photosensitive resin layer.

(photopolymerization initiator)

The photosensitive resin layer (preferably, a negative photosensitive resin layer) preferably contains a photopolymerization initiator. The photosensitive resin layer (preferably, a negative photosensitive resin layer) more preferably contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

The photopolymerization initiator initiates polymerization of the polymerizable compound by receiving activating light (e.g., ultraviolet rays and visible rays). The photopolymerization initiator is one of photoreaction initiators.

Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -aminoalkylbenzophenone structure, a photopolymerization initiator having an α -hydroxyalkylbenzophenone structure, a photopolymerization initiator having an acylphosphine oxide structure, and a photopolymerization initiator having an N-phenylglycine structure. The photopolymerization initiator is preferably at least one photopolymerization initiator selected from the group consisting of a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -aminoalkylbenzophenone structure, a photopolymerization initiator having an α -hydroxyalkylbenzophenone structure, and a photopolymerization initiator having an N-phenylglycine structure.

The photopolymerization initiator is also preferably at least one photopolymerization initiator selected from 2,4, 5-triarylimidazole dimers and derivatives thereof. In the 2,4, 5-triarylimidazole dimer and its derivative, the two 2,4, 5-triarylimidazole structures may be the same as each other or may be different from each other.

Preferred examples of the derivative of 2,4, 5-triarylimidazole dimer include 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer and 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer.

Examples of the photopolymerization initiator include those described in paragraphs 0031 to 0042 of JP 2011-95716 and paragraphs 0064 to 0081 of JP 2015-14783.

Examples of the photopolymerization initiator include 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, BASF Japan Ltd.), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetoxime) (trade name: IRGACURE OXE-02, BASF Japan Ltd.), IRGACURE OXE-03 (BASF Japan Ltd.), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (trade name: omni 379EG, IGM Resins B.V.), 2-methyl-1- (4-methylthiophenyl) -2-propanone (Omni-4-m, omni-hydroxy-2- { 3-methyl-2- [ (Omni-phenyl) methyl ] -1- (4-morpholinyl) phenyl ] -2- (Omni-ethyl-2-4-morpholinyl) phenyl ] -1-butanone (trade name: omni-3-yl) and (trade name: om-2-hydroxy-3-yl) ethyl ] -1- (2-morpholinyl) phenyl ] -2- (Om-methyl-2-morpholinyl) phenyl ] -1-butanone (trade name: om-3, and (BASF Japan L.) methyl ] -1- (2-methyl-2- (O-phenylmethyl) 2- (O-phenylketone (L) methyl) ketone (L) and L-methyl (L) ketone (L) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: omnirad 369, IGM Resins b.v.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: omnirad 1173, IGM Resins b.v.), 1-hydroxycyclohexyl phenyl ketone (trade name: omnirad 184, IGM Resins b.v.), 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: omnirad 651, IGM Resins b.v.), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (trade name: omnirad TPO H, IGM Resins b.v.), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: omnirad 819, IGM Resins b.v.), oxime ester photopolymerization initiators (trade name: lunar 6, sh holdltd.), 2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenylbisimidazole (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (trade name: omnirad H, IGM resin b.v.), bis (trade name: omnirad 819, IGM resin b.v.), oxime ester photopolymerization initiators (trade name: lunar 6, sh hold.) 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylimidazole (trade name: 2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer (trade name: m-35B-2, 35 c, 2- (2-chlorophenyl) -2, 37 b.v.), and (trade name: 2-chlorophenyl) -2, 37 b.tdb.v).

Further, examples of commercial products of photopolymerization initiators include ADEKA ARKLS NCI-930, ADEKA ARKLS NCI-730, and ADEKA ARKLS N-1919T manufactured by ADEKA CORPORATION.

The photosensitive resin layer may contain one or two or more photopolymerization initiators.

The content of the photopolymerization initiator is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and particularly preferably 1.0 mass% or more, relative to the total mass of the photosensitive resin layer. The content of the photopolymerization initiator is preferably 10 mass% or less, more preferably 5 mass% or less, relative to the total mass of the photosensitive resin layer.

(Polymer having acid groups)

The photosensitive resin layer (preferably, a negative photosensitive resin layer) preferably contains a polymer having an acid group (hereinafter, sometimes referred to as "polymer Y").

Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group, and a phosphonate group. The acid group is preferably a carboxyl group.

From the viewpoint of alkali developability, the polymer Y is preferably an alkali-soluble resin having an acid value of 60mgKOH/g or more, more preferably a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more. Examples of the carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more include carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the polymer described in paragraph 0025 of JP 2011-95716, carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the polymers described in paragraphs 0033 to 0052 of JP 2010-237589, and carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the binder polymers described in paragraphs 0053 to 0068 of JP 2016-224162. Here, the "acrylic resin" means a resin containing at least one of a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid ester. The content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester of the acrylic resin is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the total mass of the acrylic resin.

The content of the structural unit having an acid group in the polymer Y is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 12 to 30% by mass relative to the total mass of the polymer Y.

The polymer Y may have reactive groups. The reactive groups are preferably polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, a polycondensable group (e.g., a hydroxyl group and a carboxyl group), and a polyaddition-reactive group (e.g., an epoxy group and an isocyanate group).

The acid value of the polymer Y is preferably 60 to 200mgKOH/g, more preferably 100 to 200mgKOH/g, still more preferably 150 to 200mgKOH/g, from the viewpoint of alkali developability.

The weight average molecular weight of the polymer Y is preferably 1,000 or more, more preferably 10,000 or more, and further preferably 20,000 ～ 100,000.

The polymer Y may have structural units derived from non-acidic monomers. Examples of the non-acidic monomer include (meth) acrylic acid esters, ester compounds of vinyl alcohol, (meth) acrylonitrile, and aromatic vinyl compounds.

Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate.

Examples of the ester compound of vinyl alcohol include vinyl acetate.

Examples of the aromatic vinyl compound include styrene and styrene derivatives.

The non-acidic monomer is preferably methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, a styrene derivative or benzyl (meth) acrylate. The non-acidic monomer is preferably styrene, a styrene derivative or benzyl (meth) acrylate from the viewpoints of resolution, adhesion of the conductive layer to the photosensitive resin layer, etching resistance and reduction of aggregates upon development.

The side chains of the polymer Y may have a linear structure, a branched structure, or an alicyclic structure. For example, a branched structure or an alicyclic structure is introduced into the side chain of the polymer Y by using a monomer having a group having a branched structure in the side chain or a monomer having a group having an alicyclic structure in the side chain. The group having an alicyclic structure may be monocyclic or polycyclic.

Examples of the monomer having a group having a branched structure in a side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isopentyl (meth) acrylate, tert-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate and tert-octyl (meth) acrylate. Isopropyl (meth) acrylate, isobutyl (meth) acrylate or tert-butyl methacrylate is preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred.

Examples of the monomer having a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Examples of the monomer having an alicyclic structure in the side chain include (meth) acrylic esters having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Examples of the monomer having a group having an alicyclic structure in a side chain include (bicyclo [ 2.2.1 ] heptyl-2) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 3-methyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyladamantyl (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl (meth) acrylate, 3,5, 8-triethyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4, 7-menthol indene-5-yl (meth) acrylate, 3, 5-triethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, octahydro-4, 7-menthol-indene (meth) acrylate, 1-menthyl (meth) acrylate, 1-hydroxy-1-adamantyl (meth) acrylate, and the like 3-hydroxy-2, 6-trimethyl-bicyclo [ 3.1.1 ] heptyl (meth) acrylate, 3, 7-trimethyl-4-hydroxy-bicyclo [ 4.1.0 ] heptyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, and cyclohexyl (meth) acrylate. Preferably cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl (meth) acrylate or tricyclodecyl (meth) acrylate, more preferably cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate or tricyclodecyl (meth) acrylate.

The photosensitive resin layer may contain one or two or more kinds of polymers Y.

From the viewpoint of photosensitivity, the content of the polymer Y is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, and even more preferably 30 to 70 mass% with respect to the total mass of the photosensitive resin layer.

The photosensitive resin layer (preferably, a negative photosensitive resin layer) may contain a resin other than the polymer Y. Examples of the resin other than the polymer Y include polyhydroxystyrene, polyimide, polybenzoxazole and polysiloxane. The types of resins other than the polymer Y contained in the photosensitive resin layer may be one or two or more.

(polymerization inhibitor)

The photosensitive resin layer (preferably, a negative photosensitive resin layer) may contain a polymerization inhibitor.

Examples of the polymerization inhibitor include thermal polymerization inhibitors described in paragraph 0018 of Japanese patent No. 4502784. The polymerization inhibitor is preferably phenothiazine, phenoxazine, hydroquinone, tetrachlorobenzoquinone, sodium phenoindophenol, m-aminophenol or 4-methoxyphenol.

The photosensitive resin layer may contain one or more polymerization inhibitors.

The content of the polymerization inhibitor is preferably 0.01 to 3 mass%, more preferably 0.01 to 1 mass%, and even more preferably 0.01 to 0.8 mass% relative to the total mass of the photosensitive resin layer.

(Hydrogen donor)

The photosensitive resin layer (preferably, a negative photosensitive resin layer) may contain a hydrogen donor. For example, the hydrogen donor may supply hydrogen to the photopolymerization initiator.

Examples of the hydrogen donor include bis [4- (dimethylamino) phenyl ] methane, bis [4- (diethylamino) phenyl ] methane, thiol compounds, and colorless crystal violet.

The photosensitive resin layer may contain one or two or more hydrogen donors.

The content of the hydrogen donor is preferably 0.01 to 10 mass%, more preferably 0.05 to 5 mass%, and even more preferably 0.1 to 2 mass% relative to the total mass of the photosensitive resin layer.

(ultraviolet absorber)

The photosensitive resin layer (preferably, a negative photosensitive resin layer) may contain an ultraviolet absorber. The ultraviolet absorber can reduce the transmittance of the photosensitive resin layer to the exposure wavelength.

Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. The ultraviolet absorber is preferably at least one ultraviolet absorber selected from benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylethyl) phenol, 2- [ 5-chloro (2H) -benzotriazol-2-yl ] -4-methyl-6- (t-butyl) phenol, 2- (2H-benzotriazol-yl) -4, 6-di-t-amylphenol, and 2- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol. The benzotriazole-based ultraviolet absorber may be a mixture, modified product, polymer or derivative of the above-mentioned compounds.

Examples of the triazine-based ultraviolet light absorber include 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [ (hexyl) oxy ] -phenol, 2- [4- [ (2-hydroxy-3-dodecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [4- [ (2-hydroxy-3-tridecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine and 2, 4-bis (2, 4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -s-triazine. The triazine ultraviolet light absorber may be a mixture, modified product, polymer or derivative of the above-mentioned compounds.

The photosensitive resin layer may contain one or two or more ultraviolet absorbers.

From the viewpoint of resolution, the content of the ultraviolet absorber is preferably 0.1 to 5 mass%, more preferably 0.1 to 3 mass%, and even more preferably 0.1 to 2 mass% relative to the total mass of the photosensitive resin layer.

(heterocyclic Compound)

The photosensitive resin layer preferably contains a heterocyclic compound. The heterocyclic compound can contribute to improvement in dimensional stability of the conductive pattern after energization and improvement in adhesion between the conductive layer and the photosensitive resin layer.

The heterocycle in the heterocyclic compound may be monocyclic or polycyclic.

Examples of the hetero atom in the heterocyclic compound include a nitrogen atom, an oxygen atom and a sulfur atom. The heterocyclic compound preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably contains a nitrogen atom.

Examples of the heterocyclic compound include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodamine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds.

The heterocyclic compound is preferably at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodamine compound, a thiazole compound, a benzimidazole compound, and a benzoxazole compound, more preferably at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, and a benzoxazole compound, further preferably at least one compound selected from the group consisting of a triazole compound and a tetrazole compound, and particularly preferably a triazole compound.

Examples of the triazole compound and benzotriazole compound include the following compounds.

[ chemical formula 4]

[ chemical formula 5]

[ chemical formula 6]

Examples of the tetrazole compound include the following compounds.

[ chemical formula 7]

[ chemical formula 8]

Examples of the thiadiazole compound include the following compounds.

[ chemical formula 9]

Examples of the triazine compound include the following compounds.

[ chemical formula 10]

Examples of the rhodanine compound include the following compounds.

[ chemical formula 11]

Examples of the thiazole compounds include the following compounds.

[ chemical formula 12]

Examples of benzothiazole compounds include the following compounds.

[ chemical formula 13]

Examples of benzimidazole compounds include the following compounds.

[ chemical formula 14]

[ chemical formula 15]

Examples of the benzoxazole compound include the following compounds.

[ chemical formula 16]

Examples of the heterocyclic compound include a compound having an epoxy group or an oxetane group, a heterocyclic compound having an alkoxymethyl group, an oxygen-containing heterocyclic compound (for example, a cyclic ether and a cyclic ester (for example, lactone)), and a nitrogen-containing heterocyclic compound (for example, a cyclic amine and oxazoline). The heterocyclic compound may be a heterocyclic compound containing an element having an electron in the d-orbital (for example, silicon, sulfur, and phosphorus).

Examples of the compound having an epoxy group include bisphenol a type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and aliphatic epoxy resin.

The compound having an epoxy group is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin or an aliphatic epoxy resin, more preferably an aliphatic epoxy resin.

The compound having an epoxy group may be commercially available.

Examples of commercial products of the epoxy group-containing compound include JER, 828, JER1007, JER, 157S70, and JER, 157S65, manufactured by Mitsubishi Chemical Corporation.

Examples of the commercial products of the epoxy group-containing compound include those described in paragraph 0189 of Japanese patent application laid-open No. 2011-221494.

Examples of the commercial products of the epoxy group-containing compound include ADEKA RESIN EP to 4000S, EP to 4003S, EP to 4010S and EP-4011S manufactured by ADEKA CORPORATION.

Examples of the commercial products of the epoxy group-containing compounds include Nippon Kayaku Co., ltd. NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501 and EPPN-502.

Examples of the commercial products of the epoxy group-containing compound include DENACOL EX-611, EX-612, EX-614-B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX-121, EX-141, EX-145, EX-146, EX-147, EX-171 and EX-192 manufactured by Nagase ChemteX Corporation.

Examples of the commercial products of the epoxy group-containing compounds include NIPPON STEEL Chemical & Material Co., ltd. YH-300, YH-301, YH-302, YH-315, YH-324 and YH-325.

Examples of the commercial products of the epoxy group-containing compounds include CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2000, CELLOXIDE 3000, EHPE 3150, EPOLAED GT400, CELVENS B0134 and CELVENS B0177 manufactured by Daicel Corporation.

Examples of commercial products of compounds having an oxetanyl group include TOAGOSEI CO. LTD. ARON OXETANE OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ and PNOX.

The compound having an oxetanyl group is preferably used alone or in combination with the compound having an epoxy group.

The heterocyclic compound is preferably a compound having an epoxy group from the viewpoints of etching resistance and line width stability.

The photosensitive resin layer may contain one or two or more heterocyclic compounds.

From the viewpoint of resolution, the content of the heterocyclic compound is preferably 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, even more preferably 0.3 to 10 mass%, and particularly preferably 0.5 to 8 mass% relative to the total mass of the photosensitive resin layer.

The mode of heterocyclic compounds is described in International publication No. 2018/179640. The contents of the above documents are incorporated by reference into the present specification.

(sensitizer)

The photosensitive resin layer may contain a sensitizer. The sensitizer becomes an electron excited state by absorbing the activating light. For example, in a photosensitive resin layer containing a photoacid generator and a sensitizer, the sensitizer in an electron excited state comes into contact with the photoacid generator to cause an effect such as electron transfer and energy transfer heat generation. The photoacid generator generates acid under the action as described above. As a result, the exposure sensitivity is improved.

Examples of the sensitizer include compounds described in paragraphs 0139 to 0141 of International publication No. 2015/093271.

The sensitizer in the positive photosensitive resin layer is preferably at least one compound selected from the group consisting of an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a basic styryl derivative, and a distyrylbenzene derivative, and more preferably an anthracene derivative.

The anthracene derivative is preferably anthracene, 9, 10-dibutoxyanthracene, 9, 10-dichloro anthracene, 2-ethyl-9, 10-dimethoxy anthracene, 9-hydroxymethyl anthracene, 9-bromo anthracene, 9-chloro anthracene, 9, 10-dibromoanthracene, 2-ethyl anthracene or 9, 10-dimethoxy anthracene.

Examples of the sensitizer in the negative photosensitive resin layer include a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, a coumarin compound, a cyanine compound, a xanthone compound, a thioxanthone compound, an oxazole compound, a benzoxazole compound, a thiazole compound, a benzothiazole compound, a triazole compound (e.g., 1,2, 4-triazole), a stilbene compound, a triazine compound, a thiophene compound, a naphthalimide compound, a triarylamine compound, and an aminoacridine compound.

Examples of the sensitizer in the negative photosensitive resin layer include dyes and pigments. Examples of the dyes and pigments include magenta, phthalocyanine GREEN, coumarin 6, coumarin 7, coumarin 102, DOC iodide, indocarbocyanine sodium, auramine, alkoxide GREEN S, paramagenta, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite GREEN (HODOGAYA CHEMICAL co., ltd., AIZEN (registered trademark) MALACHITE GREEN), basic blue 20, and DIAMOND GREEN (HODOGAYA CHEMICAL co., ltd., AIZEN (registered trademark) DIAMOND GREEN GH).

Examples of the dye include a color-developing dye. The color-developing dye is a compound having a function of developing color by irradiation with light. Examples of the color-developing dye include leuco dyes and fluoran dyes. The color-developing dye is preferably a leuco dye.

The photosensitive resin layer may contain one or two or more sensitizers.

The content of the sensitizer is preferably 0 to 10 mass%, more preferably 0.1 to 10 mass%, based on the total mass of the positive photosensitive resin layer.

The content of the sensitizer is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% relative to the total mass of the negative photosensitive resin layer, from the viewpoint of improving the sensitivity to a light source and improving the curing speed by the balance between the polymerization speed and chain transfer.

The form of the sensitizer is described in International publication No. 2018/179640. The contents of the above documents are incorporated by reference into the present specification.

(plasticizer)

The photosensitive resin layer may contain a plasticizer. The plasticizer can adjust the plasticity of the photosensitive resin layer.

From the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.

[ chemical formula 17]

In the above structure, R represents an alkylene group having 2 to 8 carbon atoms, n represents an integer of 1 to 50, and x represents a bonding site with another atom.

If the plasticity of the positive photosensitive resin layer containing the compound having the alkyleneoxy group having the above-described structure (hereinafter, referred to as "compound X"), the polymer X1, and the photoacid generator is not improved over that of the positive photosensitive resin layer containing no compound X, the compound X does not correspond to the plasticizer in the present invention. The surfactant to be used is not generally used in an amount capable of imparting plasticity to the positive photosensitive resin layer, and therefore does not correspond to the plasticizer in the present invention.

Examples of the plasticizer include compounds having the following structures. However, the plasticizer is not limited to the following compounds.

[ chemical formula 18]

The weight average molecular weight of the plasticizer is preferably smaller than that of the polymer X1. From the viewpoint of imparting plasticity, the weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, and still more preferably 800 or more and less than 4,000.

The photosensitive resin layer may contain one or two or more plasticizers.

From the viewpoint of adhesion between the conductive layer and the photosensitive resin layer, the plasticizer content is preferably 1 to 50 mass%, more preferably 2 to 20 mass%, relative to the total mass of the photosensitive resin layer.

The manner of plasticizer is described in International publication No. 2018/179640. The contents of the above documents are incorporated by reference into the present specification.

(surfactant)

The photosensitive resin layer may contain a surfactant. The surfactant may contribute to uniformity of film thickness.

Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants (i.e., nonionic surfactant), and amphoteric surfactants. The surfactant is preferably a nonionic surfactant.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyethylene glycol, silicone surfactants, and fluorine surfactants.

Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates thereof (for example, glycerol propoxylate).

Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and propoxylates thereof (for example, glycerin ethoxylate).

Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters.

Examples of the commercial products of the nonionic surfactant include KP (Shin-Etsu Chemical Co., ltd.), POLYFLOW (KYOEISHA CHEMICAL CO., LTD.), EFTOP (JEMCO.), MEGAFACE (registered trademark, DIC CORPORATION), fluorine (Sumitomo 3M Limited), asahiguard (registered trademark, AGC Inc.), surflon (registered trademark, AGC SEIMI CHEMICAL CO., LTD.), polyFox (OMNOVA SOLUTIONS INC.), and SH-8400 (Dow Corning Toray Co., ltd.).

Examples of the commercial products of the nonionic surfactants include Pluronic L10, L31, L61, L62, 10R5, 17R2 and 25R2 manufactured by BASF corporation.

Examples of the commercial products of the nonionic surfactants include Tetronic 304, 701, 704, 901, 904, and 150R1 manufactured by BASF corporation.

Examples of the commercial product of the nonionic surfactant include Solsperse 20000 manufactured by The Lubrizol Corporation.

Examples of the commercial products of the nonionic surfactant include NCW-101, NCW-1001 and NCW-1002 manufactured by FUJIFILM Wako Pure Chemical Corporation.

Examples of the commercial products of the nonionic surfactant include TAKEMOTO OIL & FAT CO, PIONIN D-6112, D-6112-W and D-6315 manufactured by LTD.

Examples of commercial products of nonionic surfactants include Nissin Chemical co., ltd. OLFINE E1010 and Surfynol 104, 400 and 440.

The surfactant is preferably a copolymer having a weight average molecular weight (Mw) of 1,000 to 10,000 in terms of polystyrene, which contains a structural unit SA and a structural unit SB represented by the following formula I-1 and is measured by gel permeation chromatography using tetrahydrofuran as a solvent.

[ chemical formula 19]

In the formula I-1, R ⁴⁰¹ R is R ⁴⁰³ Each independently represents a hydrogen atom or a methyl group, R ⁴⁰² Represents a linear alkylene group having 1 to 4 carbon atoms, R ⁴⁰⁴ Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, p represents a number of 10 to 80 mass%, q represents a value of 20 mass% or more and 90 mass% or less, r represents an integer of 1 or more and 18 or less, s represents an integer of 1 or more and 10 or less, and x represents a bonding site with another structure.

L is preferably a branched alkylene group represented by the following formula I-2.

[ chemical formula 20]

/>

R in formula I-2 ⁴⁰⁵ An alkyl group having 1 to 4 carbon atoms. From the standpoint of compatibility, R ⁴⁰⁵ The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 2 carbon atoms or an alkyl group having 3 carbon atoms. The sum of p and q is preferably 100 mass% (i.e., p +)q＝100)。

The weight average molecular weight (Mw) of the copolymer containing the structural unit SA and the structural unit SB represented by the formula I-1 is preferably 1,500 or more and 5,000 or less.

Examples of the fluorine-based surfactant include those commercially available from DIC CORPORATION MEGAFACEF-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, 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-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K and DS-21.

Examples of the commercial products of the fluorine-based surfactant include fluorine FC430, FC431, and FC171 manufactured by Sumitomo 3M Limited.

Examples of the commercially available fluorine-based surfactant include Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 manufactured by AGC Inc.

Examples of the commercially available fluorine-based surfactant include PolyFox PF636, PF656, PF6320, PF6520 and PF7002 manufactured by OMNOVA SOLUTIONS INC.

Examples of the commercial products of the fluorine-based surfactants include Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681 and 683 manufactured by NEOS COMPANY LIMITED.

Preferred examples of the fluorine-based surfactant include an acrylic compound having a molecular structure having a functional group containing a fluorine atom, wherein the fluorine atom is volatilized by cleavage of a portion of the functional group containing a fluorine atom upon heating. Examples of such a fluorine-based surfactant include the MEGAFACEDS series (The Chemical Daily (2016, 2, 22 days) and NIKKEI BUSINESS DAILY (2016, 2, 23 days) manufactured by DIC CORPORATION). As a commercial product, MEGAFACE DS-21 can be mentioned.

Preferred fluorinated surfactants include, for example, polymers of vinyl ether compounds containing fluorine atoms and hydrophilic vinyl ether compounds having fluorinated alkyl groups or fluorinated alkylene ether groups.

The fluorine-based surfactant may be a block polymer.

The preferred fluorine-based surfactant includes, for example, a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound having a fluorine atom and a structural unit derived from a (meth) acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups).

Examples of the fluorine-based surfactant include a fluoropolymer having an ethylenically unsaturated bond-containing group in a side chain. Examples of the commercial products include those manufactured by DIC CORPORATION MEGAFACE RS-101, RS-102, RS-718K and RS-72-K.

From the viewpoint of improving the environmental suitability, the fluorine-based surfactant is preferably a surfactant derived from a substitute material of a compound having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

Examples of the silicone surfactant include linear polymers composed of siloxane bonds, and modified siloxane polymers having organic groups introduced into side chains or terminal ends.

Examples of the commercial products of silicone surfactants include Dow Corning Toray co., ltd. DOWSIL 8032 ADDITIVE, TORAY SILICONE DC PA, TORAY SILICONE SH PA, TORAY SILICONE DC PA, TORAY SILICONE SH PA, TORAY SILICONE SH PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH8400.

Examples of the commercially available silicone surfactants include Shin-Etsu Chemical Co., ltd. X-22-4952, X-22-4272, X-22-6266, KF-351A, K354-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002.

Examples of the commercial products of silicone surfactants include those manufactured by Momentive performance Materials Inc. products F-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452.

Examples of the commercial products of silicone surfactants include BYK307, BYK323, and BYK330 manufactured by BYK-Chemie GmbH.

Examples of the surfactant include surfactants described in paragraphs 0060 to 0071 of JP-A-4502784, paragraph 0017 and JP-A-2009-237362.

The photosensitive resin layer may contain one or two or more surfactants.

The content of the surfactant is preferably 10 mass% or less, more preferably 0.001 mass% to 10 mass%, and even more preferably 0.01 mass% to 3 mass% relative to the total mass of the photosensitive resin layer.

The manner of the surfactant is described in International publication No. 2018/179640. The contents of the above documents are incorporated by reference into the present specification.

(solvent)

The photosensitive resin layer may contain a solvent. For example, when the photosensitive resin layer is formed using a composition containing a solvent, the solvent may remain in the photosensitive resin layer.

Examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP 2011-221494 and the solvents described in paragraphs 0092 to 0094 of International publication No. 2018/179640. Examples of the solvent include cyclic ether solvents such as tetrahydrofuran.

The photosensitive resin layer may contain one or two or more solvents.

The content of the solvent is preferably 2 mass% or less, more preferably 1 mass% or less, and particularly preferably 0.5 mass% or less, relative to the total mass of the photosensitive resin layer.

The water content is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass% relative to the total mass of the photosensitive resin layer.

(other Components)

The photosensitive resin layer may contain other components. Examples of the other components include metal oxide particles, antioxidants, dispersants, acid-proliferation agents, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic anti-settling agents. A preferred embodiment of the other components is described in paragraphs 0165 to 0184 of Japanese unexamined patent publication No. 2014-85643. The contents of the above documents are incorporated herein by reference.

(impurity)

The photosensitive resin layer may contain impurities within a range not departing from the gist of the present invention.

Examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. The content of the halide ion, sodium ion and potassium ion is preferably within the following numerical range.

The content of impurities in the photosensitive resin layer is preferably 80ppm or less, more preferably 10ppm or less, and further preferably 2ppm or less on a mass basis. The content of impurities in the photosensitive resin layer may be 1ppb or more or 0.1ppm or more on a mass basis. The content of impurities is measured by a known method such as ICP (Inductively Coupled Plasma (inductively coupled plasma)) emission spectrometry, atomic absorption spectrometry, or ion chromatography.

Examples of the method for adjusting the content of the impurity include a method for selecting a raw material having a small content of the impurity, a method for preventing the impurity from being mixed in the process of producing the photosensitive resin layer, and a method for removing the impurity by washing.

The photosensitive resin layer preferably contains a small amount of a compound such as benzene, formaldehyde, trichloroethylene, 1, 3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide, and hexane. The content of the compound in the photosensitive resin layer is preferably 100ppm or less, more preferably 20ppm or less, and further preferably 4ppm or less on a mass basis. The content of the compound may be 10ppb or more or 100ppb or more on a mass basis. The content of the compound is determined by a known method. The content of the compound can be adjusted by the same method as that of the above-described method of adjusting the content of the impurity.

The photosensitive resin layer may contain a monomer used for producing the resin. Examples of the monomer include monomers corresponding to the structural units of the alkali-soluble resin.

The content of the monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and still more preferably 500 mass ppm or less, relative to the total mass of the alkali-soluble resin, from the viewpoints of patterning property and reliability. The content of the monomer may be 1 mass ppm or more or 10 mass ppm or more with respect to the total mass of the alkali-soluble resin.

The content of the monomer is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and even more preferably 100 mass ppm or less, relative to the total mass of the photosensitive resin layer, from the viewpoints of patterning property and reliability. The content of the monomer may be 0.1 mass ppm or more or 1 mass ppm or more relative to the total mass of the photosensitive resin layer.

The amount of the monomer remaining in synthesizing the alkali-soluble resin by the polymer reaction is also preferably adjusted within the above range. For example, in the case of synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably adjusted within the above-mentioned range.

The amount of the monomer is measured by a known method such as liquid chromatography or gas chromatography.

(thickness of photosensitive resin layer)

The thickness of the photosensitive resin layer is not limited. The average thickness of the photosensitive resin layer is preferably 0.5 μm or more, more preferably 1 μm or more, from the viewpoint of uniformity of film thickness. The average thickness of the photosensitive resin layer is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less from the viewpoint of resolution. The average thickness of the photosensitive resin layer is measured by a method based on the above-described method for measuring the average thickness of the substrate.

(method for Forming photosensitive resin layer)

Examples of the method for forming the photosensitive resin layer include a coating method and a method using a transfer material.

For example, the coating method may form the photosensitive resin layer by applying the photosensitive resin layer-forming composition onto the conductive layer. The coated photosensitive resin layer-forming composition may be dried by a known method as required.

Examples of the method for producing the composition for forming a photosensitive resin layer include a method in which a raw material and a solvent for forming a target photosensitive resin layer are mixed in an arbitrary ratio. The mixing method may be a known method. The composition for forming a photosensitive resin layer may be filtered using a filter (for example, a filter having a pore size of 0.2 μm).

Examples of the solvent include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides and lactones.

Examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP 2011-221494 and the solvents described in paragraphs 0092 to 0094 of International publication No. 2018/179640. The contents of these documents are incorporated by reference into this specification.

Benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate or propylene carbonate may be added to the solvent as required.

The solvent is preferably a solvent having a boiling point of 130 ℃ or more and less than 160 ℃, a solvent having a boiling point of 160 ℃ or more, or a mixture thereof.

Examples of the solvent having a boiling point of 130℃or higher and lower than 160℃include propylene glycol monomethyl ether acetate (boiling point 146 ℃), propylene glycol monoethyl ether acetate (boiling point 158 ℃), propylene glycol methyl n-butyl ether (boiling point 155 ℃) and propylene glycol methyl n-propyl ether (boiling point 131 ℃).

Examples of the solvent having a boiling point of 160℃or higher include ethyl 3-ethoxypropionate (boiling point 170 ℃), diethylene glycol methylether (boiling point 176 ℃), propylene glycol monomethyl ether propionate (boiling point 160 ℃), dipropylene glycol methyl ether acetate (boiling point 213 ℃), 3-methoxybutyl ether acetate (boiling point 171 ℃), diethylene glycol diethyl ether (boiling point 189 ℃), diethylene glycol dimethyl ether (boiling point 162 ℃), propylene glycol diacetate (boiling point 190 ℃), diethylene glycol monoethyl ether acetate (boiling point 220 ℃), dipropylene glycol dimethyl ether (boiling point 175 ℃) and 1, 3-butanediol diacetate (boiling point 232 ℃).

The photosensitive resin layer-forming composition may contain one or two or more solvents. The photosensitive resin layer-forming composition preferably contains two or more solvents. In the case where two or more solvents are used simultaneously, for example, propylene glycol monoalkyl ether acetates and dialkyl ethers, diacetic esters and diethylene glycol dialkyl ethers or esters and butanediol alkyl ether acetates are preferably used simultaneously.

The content of the solvent is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin layer-forming composition.

Examples of the method for coating the photosensitive resin layer-forming composition include slit coating, spin coating, curtain coating, and inkjet coating. The method of coating the photosensitive resin layer-forming composition is preferably slot coating.

The photosensitive resin layer is preferably formed using a transfer material. For example, the step of forming the photosensitive resin layer preferably includes: a step of preparing a transfer material including a temporary support and a photosensitive resin layer; and adhering the photosensitive resin layer of the transfer material to the conductive layer. In the present invention, "preparing a transfer material" means making the transfer material usable.

Examples of the temporary support include a glass substrate, a resin film, and paper. The temporary support is preferably a resin film from the viewpoint of strength and flexibility. Examples of the resin film include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. The temporary support is preferably a polyethylene terephthalate film, more preferably a biaxially stretched polyethylene terephthalate film.

The temporary support may be a film that is flexible and does not undergo significant deformation, shrinkage or elongation under pressure or under pressure and heat. Examples of such a film include a polyethylene terephthalate film (for example, a biaxially stretched polyethylene terephthalate film), a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film. The temporary support is preferably a biaxially stretched polyethylene terephthalate film. The film used as the temporary support preferably has no deformation such as wrinkles or scratches.

The temporary support preferably has high transparency from the viewpoint that the photosensitive resin layer can be pattern-exposed via the temporary support. The transmittance of the temporary support to a wavelength of 365nm is preferably 60% or more, more preferably 70% or more.

The haze of the temporary support is preferably small from the viewpoints of the pattern formability at the time of pattern exposure via the temporary support and the transparency of the temporary support. The haze of the temporary support is preferably 2% or less, more preferably 0.5% or less, and still more preferably 0.3% or less.

From the viewpoints of patterning property at the time of pattern exposure via the temporary support and transparency of the temporary support, the number of particles, foreign matters, and defects contained in the temporary support is preferably small. The number of particles, foreign matters and defects having a diameter of 1 μm or more is preferably 50/10 mm ² Hereinafter, more preferably 10 pieces/10 mm ² Hereinafter, it is more preferably 3/10 mm ² Hereinafter, it is particularly preferably 0/10 mm ² 。

The average thickness of the temporary support is preferably 5 μm to 200 μm. The average thickness of the temporary support is preferably 10 μm to 150 μm, more preferably 10 μm to 50 μm, from the viewpoints of ease of handling and versatility. The average thickness of the temporary support is measured by a method based on the above-described measurement method of the average thickness of the substrate.

Preferred modes of the temporary support are described in paragraphs 0017 to 0018 of Japanese patent application laid-open No. 2014-85643, paragraphs 0019 to 0026 of Japanese patent application laid-open No. 2016-27363, paragraphs 0041 to 0057 of International publication No. 2012/081680, and paragraphs 0029 to 0040 of International publication No. 2018/179370. The contents of these documents are incorporated herein by reference.

The transfer material may further include a protective film. For example, the transfer material may include a temporary support, a photosensitive resin layer, and a protective film in this order.

Examples of the protective film include a resin film and paper. The protective film is preferably a resin film from the viewpoint of strength and flexibility. Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. The resin film is preferably a polyethylene film, a polypropylene film or a polyethylene terephthalate film.

The protective film may have an average thickness of 1 μm to 2mm. The average thickness of the protective film is measured by a method based on the above-described measurement method of the average thickness of the substrate.

The transfer material may also include other layers. Examples of the other layer include a thermoplastic resin layer and an intermediate layer.

The thermoplastic resin layer is preferably disposed between the temporary support and the photosensitive resin layer.

The thermoplastic resin layer preferably contains a thermoplastic resin.

The thermoplastic resin is preferably an alkali-soluble resin. Examples of the alkali-soluble resin include acrylic resins, polystyrene, styrene-acrylic copolymers, polyurethane, polyvinyl alcohol, polyvinyl formal, polyamide, polyester, epoxy resins, polyacetal, polyhydroxystyrene, polyimide, polybenzoxazole, polysiloxane, polyethyleneimine, polyallylamine, and polyalkylene glycol.

The alkali-soluble resin is preferably an acrylic resin from the viewpoints of developability and adhesion. Examples of the acrylic resin include resins containing at least one structural unit 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. In the acrylic resin, the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylamide is preferably 50 mass% or more with respect to the total mass of the acrylic resin. In the acrylic resin, the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, relative to the total mass of the acrylic resin.

From the viewpoints of developability and adhesion, the alkali-soluble resin is preferably a resin containing a structural unit derived from (meth) acrylic acid.

The alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group and a phosphonate group, and a carboxyl group is preferable.

From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 40mgKOH/g or more, more preferably a carboxyl group-containing acrylic resin having an acid value of 40mgKOH/g or more. The acid value of the alkali-soluble resin is preferably 300mgKOH/g or less, more preferably 250mgKOH/g or less, still more preferably 200mgKOH/g or less, particularly preferably 160mgKOH/g or less.

Examples of the carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more include alkali-soluble resins as carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the polymer described in paragraph 0025 of JP 2011-095716, carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the polymer described in paragraphs 0033 to 0052 of JP 2010-237589, and carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more in the binder polymer described in paragraphs 0053 to 0068 of JP 2016-224162. The copolymerization ratio of the structural unit having a carboxyl group in the carboxyl group-containing acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 12 to 30% by mass, relative to the total mass of the acrylic resin.

The alkali-soluble resin may have a reactive group. Examples of the reactive group include an addition polymerizable group. Examples of the reactive group include an ethylenically unsaturated group polycondensation group (for example, hydroxyl group and carboxyl group) and a polyaddition reactive group (for example, epoxy group and (block) isocyanate group).

The alkali-soluble resin preferably has a weight average molecular weight (Mw) of 1,000 or more, more preferably 1 to 10 tens of thousands, particularly preferably 2 to 5 tens of thousands.

The thermoplastic resin layer may contain one or two or more alkali-soluble resins.

The content of the alkali-soluble resin is preferably 10 to 99 mass%, more preferably 20 to 90 mass%, even more preferably 40 to 80 mass%, and particularly preferably 50 to 75 mass% with respect to the total mass of the thermoplastic resin layer from the viewpoints of developability and adhesion.

The thermoplastic resin layer preferably contains pigment B. Pigment B is a pigment having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm at the time of color development and having a maximum absorption wavelength changed by an acid, a base or a radical. From the viewpoints of visibility and resolution of the exposed portion and the non-exposed portion, the dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid. From the viewpoint of visibility and resolution of the exposed portion and the non-exposed portion, the thermoplastic resin layer preferably contains a dye whose maximum absorption wavelength is changed by an acid and a compound that generates an acid by light.

The thermoplastic resin layer may contain one or two or more pigments B.

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

The content of the pigment B indicates the content of the pigment when all of the pigment B contained in the thermoplastic resin layer is in a color-developed state. Hereinafter, a method for determining the content of the dye B will be described by taking a dye developed by a radical as an example. A solution in which 0.001g of a dye was dissolved in 100mL of methyl ethyl ketone and a solution in which 0.01g of a dye was dissolved in 100mL of methyl ethyl ketone were prepared. To each solution, a photo radical polymerization initiator "Irgacure OXE01" (trade name, BASF Japan ltd.) was added, and radicals were generated by irradiation of light of 365nm, thereby bringing all pigments into a color development state. Then, the absorbance of each solution having a liquid temperature of 25℃was measured under an air atmosphere using a spectrophotometer (UV 3100, SHIMADZU CORPORATION), and a calibration curve was prepared. Next, the absorbance of the solution was measured in the same manner as described above, except that 0.1g of the thermoplastic resin layer was dissolved in methyl ethyl ketone instead of the pigment. The amount of the pigment contained in the thermoplastic resin layer was calculated from the absorbance of the solution containing the thermoplastic resin layer and the calibration curve.

The thermoplastic resin layer may contain a compound C. Compound C is a compound that generates an acid, a base, or a radical by light. The compound C is preferably a compound that generates an acid, a base, or a radical upon receiving an activating light such as ultraviolet rays or visible rays. Photoacid generators, photobase generators, and photo radical polymerization initiators (i.e., photo radical generators) may be used as compound C.

From the viewpoint of resolution, the thermoplastic resin layer may contain a photoacid generator. Examples of the photoacid generator include photo-cationic polymerization initiators.

From the viewpoints of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds. The photoacid generator preferably contains an oxime sulfonate compound from the viewpoints of sensitivity, resolution and adhesion. Examples of the photoacid generator include photoacid generators having the following structures.

[ chemical formula 21]

The thermoplastic resin layer may contain a photo radical polymerization initiator. The photo radical polymerization initiator may be selected from known photo radical polymerization initiators. The photo radical polymerization initiator may be selected from the photo polymerization initiators described above.

The thermoplastic resin layer may contain a photobase generator. Examples of the photobase generator include 2-nitrobenzyl cyclohexyl carbamate, triphenylmethanol, o-carbamoyl hydroxyamide, o-carbamoyl oxime, [ [ (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-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, cobalt (III) tris (triphenylmethyl borate), 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.

The thermoplastic resin layer may contain one or two or more compounds C.

From the viewpoint of visibility and resolution of the exposed portion and the non-exposed portion, the content of the compound C is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass% with respect to the total mass of the thermoplastic resin layer.

From the viewpoints of resolution, adhesion and developability, the thermoplastic resin layer preferably contains a plasticizer.

The molecular weight of the plasticizer is preferably smaller than that of the alkali-soluble resin. The molecular weight (e.g., weight average molecular weight) of the plasticizer is preferably 200 to 2,000.

The plasticizer may be selected from compounds which are compatible with the alkali-soluble resin and exhibit plasticity. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound having an alkyleneoxy group, more preferably a polyalkylene glycol compound. The alkyleneoxy group preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

The plasticizer preferably contains a (meth) acrylate compound from the viewpoints of resolution and storage stability. From the viewpoints of compatibility, resolution, and adhesion, it is preferable that the alkali-soluble resin is an acrylic resin, and the plasticizer contains a (meth) acrylate compound. Examples of the (meth) acrylate compound used as the plasticizer include (meth) acrylate compounds which are one of the above-mentioned polymerizable compounds.

In the case where the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer, it is preferable that the (meth) acrylate compound does not polymerize in an exposed portion after exposure from the viewpoint of adhesion.

The (meth) acrylate compound used as the plasticizer is preferably a compound having two or more (meth) acryloyl groups from the viewpoints of resolution, adhesion and developability.

The (meth) acrylate compound used as the plasticizer is preferably a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound.

The thermoplastic resin layer may contain one or two or more plasticizers.

The content of the plasticizer is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and even more preferably 20 to 50% by mass, based on the total mass of the thermoplastic resin layer, from the viewpoints of resolution, adhesion, and developability.

The thermoplastic resin layer may contain a sensitizer. Examples of the sensitizer include the sensitizers described as components of the photosensitive resin layer.

The thermoplastic resin layer may contain one or two or more sensitizers.

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

The thermoplastic resin layer may contain other components. Examples of the other component include surfactants. Examples of the surfactant include surfactants described as components of the photosensitive resin layer.

From the viewpoint of adhesion, the average thickness of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more. The average thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less from the viewpoints of developability and resolution. The average thickness of the thermoplastic resin layer is measured by a method based on the above-described measurement method of the average thickness of the substrate.

The thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A2014-085643. The contents of the above documents are incorporated by reference into the present specification.

The intermediate layer is preferably disposed between the temporary support and the photosensitive resin layer. The intermediate layer is preferably disposed between the thermoplastic resin and the photosensitive resin layer.

Examples of the intermediate layer include an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in JP-A-5-072724. If the intermediate layer is an oxygen barrier layer, the sensitivity at the time of exposure is improved, and the time load of the exposure machine is reduced. As a result, productivity improves. The oxygen barrier layer used as the intermediate layer may be selected from known oxygen barrier layers. The oxygen barrier layer is preferably an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (for example, a 1 mass% aqueous solution of sodium carbonate at 22 ℃).

Examples of the intermediate layer include a water-soluble resin layer. The water-soluble resin layer preferably contains a water-soluble resin.

Examples of the water-soluble resin include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, and polyamide resins.

Examples of the water-soluble resin include a copolymer of (meth) acrylic acid and a vinyl compound. The copolymer of (meth) acrylic acid/vinyl compound is preferably a copolymer of (meth) acrylic acid/(meth) acrylic acid allyl ester, more preferably a copolymer of methacrylic acid/methacrylic acid allyl ester. In the case where the water-soluble resin is a copolymer of (meth) acrylic acid/vinyl compound, the ratio (mol%) of (meth) acrylic acid/vinyl compound is preferably 90/10 to 20/80, more preferably 80/20 to 30/70.

The weight average molecular weight of the water-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, and still more preferably 10,000 or more. The weight average molecular weight of the water-soluble resin is preferably 200,000 or less, more preferably 100,000 or less, and further preferably 50,000 or less. The dispersity (Mw/Mn) of the water-soluble resin is preferably 1 to 10, more preferably 1 to 5.

From the viewpoint of further improving the interlayer mixture inhibition ability of the water-soluble resin layer, the resin in the water-soluble resin layer is preferably different from the resin contained in the layer adjacent to the water-soluble resin layer.

From the viewpoint of further improving the oxygen barrier property and interlayer mixing inhibition ability, the water-soluble resin preferably contains polyvinyl alcohol, more preferably contains polyvinyl alcohol and polyvinylpyrrolidone.

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

The content of the water-soluble resin is preferably 50 mass% or more, more preferably 70 mass% or more, still more preferably 80 mass% or more, and particularly preferably 90 mass% or more, relative to the total mass of the water-soluble resin layer, from the viewpoint of further improving the oxygen barrier property and interlayer mixing inhibition ability. The upper limit of the content of the water-soluble resin is not limited. The content of the water-soluble resin is preferably 99.9 mass% or less, more preferably 99.8 mass% or less, relative to the total mass of the water-soluble resin layer.

The intermediate layer may contain a known additive such as a surfactant, if necessary. Examples of the surfactant include surfactants described as components of the photosensitive resin layer.

The average thickness of the intermediate layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm, from the viewpoints of oxygen barrier property, interlayer mixing inhibition ability, and removal time at the time of development. The average thickness of the intermediate layer is measured by a method based on the measurement method of the average thickness of the substrate described above.

The method of manufacturing the transfer material is not limited as long as the target transfer material can be obtained. For example, the transfer material is produced by applying a photosensitive resin layer-forming composition to a temporary support. For example, the transfer material is manufactured as follows: a photosensitive resin layer is formed by applying a photosensitive resin layer-forming composition onto a protective film, and then a temporary support is disposed on the photosensitive resin layer. The coated photosensitive resin layer-forming composition may be dried by a known method as required.

The lamination of the conductive layer of the laminate and the photosensitive resin layer of the transfer material is preferably performed by pressing and heating with a roller. For example, the pressure (e.g., line pressure) is adjusted in the range of 1,000N/m to 10,000N/m. For example, the temperature is adjusted in the range of 40℃to 130 ℃. When the pressure or temperature is adjusted to be equal to or higher than the lower limit of the above range, bubbles remaining between the conductive layer and the photosensitive resin layer are reduced. When the pressure is adjusted to be equal to or less than the upper limit of the above range, deformation of the photosensitive resin layer can be prevented. When the temperature is adjusted to be equal to or lower than the upper limit of the above range, decomposition or modification of the photosensitive resin layer can be prevented. When the conductive layer of the laminate and the photosensitive resin layer of the transfer material are bonded, for example, a laminator, a vacuum laminator, or an automatic cutting laminator can be used. The lamination of the conductive layer of the laminate and the photosensitive resin layer of the transfer material may be performed by roll-to-roll lamination.

A specific example of the preparation step and the photosensitive resin layer forming step will be described with reference to fig. 1. Fig. 1 is a schematic diagram of a preparation step and a photosensitive resin layer forming step in a method for manufacturing a resin pattern according to an embodiment.

Fig. 1 (a) shows a specific example of the preparation process. A laminate including the substrate 10 and the conductive layer 20 is prepared. The conductive layer 20 has a 2 nd surface 20a on the opposite side of the 1 st surface facing the substrate 10.

Fig. 1 (b) and 1 (c) show specific examples of the steps for forming the photosensitive resin layer. The photosensitive resin layer 30 shown in fig. 1 b is a part of a transfer material (not shown). That is, the step of forming the photosensitive resin layer shown in fig. 1 (b) and 1 (c) is performed using a transfer material. The photosensitive resin layer 30 has a 3 rd surface 30a facing the conductive layer 20. The surface free energy γs1 of the 2 nd surface 20a of the conductive layer 20 and the surface free energy γr of the 3 rd surface 30a of the photosensitive resin layer 30 satisfy the relationship of |γs1- γr|+.12. The photosensitive resin layer 30 is adhered to the conductive layer 20 and disposed on the 2 nd surface 20a of the conductive layer 20. The 3 rd surface 30a of the photosensitive resin layer 30 is in contact with the 2 nd surface 20a of the conductive layer 20.

A specific example of the preparation step and the photosensitive resin layer forming step will be described with reference to fig. 2. Fig. 2 is a schematic diagram of a preparation step and a photosensitive resin layer forming step in a method for manufacturing a resin pattern according to an embodiment. The process shown in fig. 2 is the same as that shown in fig. 1, except for the following description. In the following description, the overlapping matters with the description of fig. 1 are omitted.

Fig. 2 (a) shows a specific example of the preparation step. A laminate including the substrate 10 and the conductive layer 20 is prepared. The conductive layer 20 is formed by bringing a solution (not shown) containing an organic substance and a solvent into contact with the conductive layer 21. The conductive layer 21 corresponds to the conductive layer (a) according to the present invention. The conductive layer 21 is disposed on the substrate 10. The conductive layer 21 has a 2 nd surface 21a on the opposite side of the 1 st surface facing the substrate 10. A solution (not shown) containing an organic substance and a solvent is applied to the conductive layer 21. The applied solution is in contact with at least the 2 nd surface 21a of the conductive layer 21. The solution attached to the conductive layer 21 is dried. The 2 nd surface 21a of the conductive layer 21 subjected to the solution treatment forms the 2 nd surface 2a of the conductive layer 20.

[ Exposure procedure ]

In the exposure step, the photosensitive resin layer is subjected to pattern exposure. The term "pattern-exposing the photosensitive resin layer" means exposing the photosensitive resin layer in a pattern. That is, in the exposure step, an exposed portion and a non-exposed portion are formed in the photosensitive resin layer.

The positional relationship between the exposed portion and the non-exposed portion is not limited. For example, the positional relationship between the exposed portion and the non-exposed portion depends on the shape and size of the target resin pattern.

For example, the light source is selected from light sources that irradiate light capable of exposing the photosensitive resin layer. Examples of the light source include an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode (light emitting diode)).

Examples of the wavelength of light irradiated to the photosensitive resin layer include 365nm, 405nm, and 436nm. The wavelength of light irradiated to the photosensitive resin layer preferably includes 365nm, 405nm or 436nm.

The exposure is preferably 5mJ/cm ² ～200mJ/cm ² More preferably 10mJ/cm ² ～1OOmJ/cm ² 。

Preferred modes of the light source, the exposure amount and the exposure method are described in, for example, paragraphs 0146 to 0147 of International publication No. 2018/155193. The contents of the above documents are incorporated by reference into the present specification.

Examples of the exposure method include a contact exposure method and a noncontact exposure method. Examples of the non-contact exposure method include a short-distance exposure method, a lens-based or mirror-based projection exposure (projection exposure) method, and a direct exposure (direct drawing exposure) method using a laser beam. In the projection exposure system of the lens system or the mirror system, an exposure machine having a Numerical Aperture (NA) of an appropriate lens can be used according to a required resolution and focal depth. Examples of the direct exposure method include a method of directly drawing a photosensitive resin layer and a method of performing reduced projection exposure on the photosensitive resin layer through a lens. From the viewpoint of reducing the influence on the photomask and the photosensitive resin layer, exposure is preferably performed by direct drawing exposure or projection exposure.

The exposure may be performed using a photomask. The photomask may be used in contact with the surface of the exposure target. The photomask may be used close to the surface of the exposure target without being in contact with the surface of the exposure target. From the viewpoint of resolution, exposure is preferably performed by bringing a photomask into contact with the surface of the exposure target.

In the case where the photosensitive resin layer is formed using a transfer material, exposure to light may be performed after the temporary support is peeled off. In the case where the photosensitive resin layer is formed using a transfer material, exposure to light may be performed before the temporary support is peeled off. In the latter method, for example, the photosensitive resin layer is exposed to light through a temporary support, and the temporary support is peeled off after the exposure. In order to prevent contamination of the photomask and to avoid the influence of foreign matter adhering to the photomask on exposure, it is preferable to expose the photosensitive resin layer through the temporary support without peeling off the temporary support.

The exposure may be performed under atmospheric air. The exposure may also be performed under reduced pressure. The exposure may also be performed under vacuum.

The exposure may be performed by interposing a liquid such as water between the light source and the exposure target.

[ developing Process ]

In the developing step, the photosensitive resin layer is developed to form a resin pattern.

The developing method is not limited. The developing method may be selected from known methods. As a developing method, for example, a method using a developing solution can be cited. The developer can remove an object having relatively high solubility to the developer.

The developer may be selected from known developers. Examples of the developer include those described in JP-A-5-72724. Examples of the preferable developer include the developer described in paragraph 0194 of International publication No. 2015/093271.

The developer is preferably an aqueous alkali solution containing a compound having a pKa of 7 to 13. The concentration of the compound having a pKa of 7 to 13 is preferably 0.05mol/L to 5mol/L.

The developer may contain other components. Examples of the other component include an organic solvent and a surfactant which can be mixed with water.

The temperature of the developer is preferably 20 to 40 ℃.

Examples of the development method include spin-coating immersion development, shower development, spin development, and immersion development.

As an example of the development method, the shower development will be described. For example, in the case where the photosensitive resin layer is a negative type photosensitive resin layer, the unexposed portion of the photosensitive resin layer can be removed by spraying a developer to the photosensitive resin layer after exposure using a shower. As a method for removing the development residues, for example, a method of spraying a cleaning agent by a shower and wiping with a brush is mentioned.

The developing process may include a process of heat-treating the resin pattern (also referred to as "post baking"). The pressure of the heat treatment is preferably 8.1kPa to 121.6kPa, more preferably 8.1kPa to 114.6kPa, and still more preferably 8.1kPa to 101.3kPa. The temperature of the heat treatment is preferably 20 to 250 ℃, more preferably 30 to 170 ℃, and still more preferably 50 to 150 ℃. The time for the heat treatment is preferably 1 to 30 minutes, more preferably 2 to 10 minutes, and still more preferably 2 to 4 minutes. The heat treatment may be performed in an air environment. The heat treatment may be performed in a nitrogen substitution environment.

The resin pattern obtained by the method as described above preferably includes a resin pattern having a line width of 20 μm or less, more preferably includes a resin pattern having a line width of 10 μm or less, still more preferably includes a resin pattern having a line width of 8 μm or less, and particularly preferably includes a resin pattern having a line width of 5 μm or less.

< method for producing conductive Pattern >

A method for producing a conductive pattern according to an embodiment of the present invention includes the method for producing a resin pattern described in the above item "method for producing a resin pattern". Specifically, the method for manufacturing a conductive pattern according to an embodiment of the present invention includes the following (1) to (3) in this order.

(1) A step of forming a resin pattern by the method for producing a resin pattern described in the above item of "method for producing a resin pattern" (hereinafter, sometimes referred to as "step for forming a resin pattern").

(2) A step of forming a conductive pattern by etching the conductive layer using the resin pattern as a mask (hereinafter, sometimes referred to as an "etching step").

(3) A step of removing the resin pattern (hereinafter, sometimes referred to as "removing step").

[ step of Forming resin Pattern ]

In the step of forming a resin pattern, the resin pattern is formed by the method of manufacturing a resin pattern described in the item "method of manufacturing a resin pattern" above. The preferred mode of the resin pattern forming step is the same as the preferred mode of the resin pattern manufacturing method described in the above item "method of manufacturing a resin pattern".

[ etching procedure ]

In the etching step, the conductive layer is etched using the resin pattern as a mask to form a conductive pattern.

The conductive pattern is formed by removing the metal nanomaterial in the region not protected by the resin pattern at the time of etching. That is, according to etching of the conductive layer, the conductive pattern is formed of a metal nanomaterial contained in the conductive layer protected by the resin pattern.

The etching method is not limited. Examples of the etching method include the methods described in paragraphs 0209 to 0210 of Japanese patent application laid-open No. 2017-120435 and the methods described in paragraphs 0048 to 0054 of Japanese patent application laid-open No. 2010-152155. As an etching method, for example, wet etching in which an object is immersed in an etching liquid is given. Examples of the etching method include dry etching such as plasma etching. From the viewpoint of productivity, the etching is preferably wet etching. From the viewpoint of resolution, the etching is preferably dry etching.

The kind of the etching liquid used for wet etching may be selected according to the etching object. Examples of the etching liquid include an acidic etching liquid and an alkaline etching liquid.

Examples of the acidic etching solution include an aqueous solution containing an acidic component and a salt. Examples of the acidic component include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid. The acidic etching solution may contain one or two or more acidic components. Examples of the salt Include Iron (II) chloride, iron (III) chloride, iron (II) nitrate, iron (III) nitrate, iron (II) sulfate, iron (III) sulfate, ammonium fluoride, and potassium permanganate. The acidic etching solution may contain one or two or more salts.

Examples of the alkaline etching liquid include an aqueous solution containing an alkali component and a salt. Examples of the alkali component include sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and salts of an organic amine (for example, tetramethylammonium hydroxide). The alkaline etching solution may contain one or two or more alkali components. Examples of the salt include potassium permanganate. The alkaline etching solution may contain one or two or more salts.

The etching liquid may contain an organic solvent and a surfactant in order to control the etching rate and the shape of the etching object.

[ removal Process ]

In the removing step, the resin pattern is removed.

As a method for removing the resin pattern, for example, a method for removing the resin pattern using a chemical is cited. The resin pattern may be dissolved in the chemical. The resin pattern may also be dispersed in the chemical.

The method of removing the resin pattern is preferably a method of removing the resin pattern using a removing liquid. For example, the resin pattern is removed by immersing the substrate having the resin pattern in a removing liquid.

The temperature of the removing liquid is preferably 30 to 80 ℃, more preferably 50 to 80 ℃.

The immersion time of the resin pattern in the removing liquid is preferably 1 to 30 minutes.

From the viewpoint of removability, the removal liquid preferably contains 30% by mass or more of water, more preferably 50% by mass or more of water, and still more preferably 70% by mass or more of water.

The removing liquid preferably contains an inorganic base component or an organic base component. Examples of the inorganic alkali component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

From the viewpoint of removability, the removal liquid preferably contains an organic base component, and more preferably contains an amine compound.

From the viewpoint of removability, the content of the organic base component is preferably 0.01 to 20 mass%, more preferably 0.1 to 10 mass%, relative to the total mass of the removing liquid.

From the viewpoint of removability, the removing liquid preferably contains a surfactant. The surfactant may be selected from known surfactants.

From the viewpoint of removability, the content of the surfactant is preferably 0.1 to 10% by mass based on the total mass of the removing liquid.

The removing liquid preferably contains a water-soluble organic solvent. Examples of the water-soluble organic solvent include dimethyl sulfoxide, lower alcohol, glycol ether and N-methylpyrrolidone.

Examples of the removing liquid include a stripping liquid described in JP-A-11-021483, JP-A-2002-129067, JP-A-07-028254, JP-A-2001-188363, JP-A-04-048633 and JP-A-5318773.

Examples of the method of bringing the removing liquid into contact with the resin pattern include a spraying method, and a spin-coating immersing method.

[ other procedures ]

The method of manufacturing the conductive pattern may further include other steps.

The method of manufacturing the conductive pattern may include a step of cleaning the conductive pattern. As the cleaning method, for example, a method of cleaning the conductive pattern using pure water is mentioned. The washing time may be 10 seconds to 300 seconds.

The method of manufacturing the conductive pattern may include a step of drying the conductive pattern. As a drying method, for example, a method of drying a conductive pattern using a blower is mentioned. The pressure of the blower is preferably 0.1kg/cm ² ～5kg/cm ² 。

The method for producing the conductive pattern may include a step of performing a treatment for reducing the visible ray reflectance of a part or all of the conductive pattern. As the treatment for reducing the reflectance of visible light, for example, an oxidation treatment is given. For example, the oxidation treatment may reduce the visible reflectance by converting copper to copper oxide. A preferable mode of the treatment for reducing the reflectance of visible light is described in, for example, paragraphs 0017 to 0025 of jp 2014-150118 a, paragraphs 0041, 0042, 0048 and 0058 of jp 2013-206315 a. The contents of these documents are incorporated by reference into this specification.

[ use ]

The use of the conductive pattern formed through the above-described steps is not particularly limited. The conductive pattern can be applied to various uses. Examples of the application of the conductive pattern include a display device, a printed wiring board, a semiconductor package substrate, and an input device. As an input device, for example, a touch panel is given. The touch panel is preferably a capacitive touch panel. For example, the input device is suitable for a display device. Examples of the display device include an organic electroluminescence display device and a liquid crystal display device. A preferable application of the conductive pattern is, for example, a flexible display device, and particularly a flexible touch panel.

Examples

The present invention will be described in detail with reference to examples. Unless otherwise specified, "parts" and "%" are based on mass. The matters described in the following examples may be appropriately modified within the scope of the present invention.

< examples 1 to 31 and comparative example 1>

[ production of laminate and surface modification of conductive layer ]

As a substrate, a film (ClearOhm, cambrios Technologies Corporation) including a polyethylene terephthalate film and a conductive layer containing silver nanowires and a resin was prepared (laminate 8 in table 1). The conductive layer has a transmittance of 92% for light having a wavelength of 380nm to 780 nm. The average thickness of the conductive layer was 0.025. Mu.m. The conductive layer has a 1 st surface facing the substrate and a 2 nd surface opposite to the 1 st surface. The contact angle of distilled water with respect to the 2 nd surface of the conductive layer was 75 °, and the contact angle of diiodomethane with respect to the 2 nd surface of the conductive layer was 60 °. Surface free calculated by Owens and Wendt method from these contact angles Can be 34.3mJ/m ² . The contact angles of distilled water and diiodomethane were average values of contact angles measured 3 times using a contact angle meter (Dropmaster 500, kyowa Interface Science co., ltd.). The amount of distilled water and diiodomethane added was 3.0. Mu.L. The time from the addition of distilled water and diiodomethane was 20 seconds. The contact angle was measured at 25 ℃.

The coating conditions of the surface modifying composition described in table 1 were determined by the following method. The surface modifying composition was coated on a polyethylene terephthalate film (Lumirror #100-S10, TORAY INDUSTRIES, INC.) using a spin coater (MS-B100, MIKASA CO., LTD). The coated surface-modifying composition was dried in an oven at 100℃and then at 600mJ/cm using an exposure machine (M-IS, MIKASA CO., LTD) ² Exposure was performed, and finally post-baking was performed for 30 minutes using a convection oven at 150 ℃. In the above method, the coating amount was determined such that the film thickness of the surface modifying composition after drying was 40 nm. The composition of the surface modifying composition is shown in Table 1. The unit of the amount of each compound shown in table 1 represents parts by mass.

According to the description in table 1, the surface modification of the conductive layer was performed by the following method. According to the coating conditions described above, the surface modifying composition is coated on the 2 nd surface of the conductive layer. The coated surface-modifying composition was dried in an oven at 100℃and then at 600mJ/cm using an exposure machine (M-1S, MIKASA CO., LTD.) ² Exposure was performed, and finally post-baking was performed for 30 minutes using a convection oven at 150 ℃. The average thickness of the surface-modified conductive layer was 0.05 μm.

Table 1 shows the characteristics (specifically, contact angle and surface free energy) of the 2 nd surface of the surface-modified conductive layer or the 2 nd surface of the non-surface-modified conductive layer in each laminate.

The following abbreviations described in table 1 have the following meanings, respectively.

XA-1: benzyl methacrylate/methacrylic acid=70/30 (mass%) copolymer (molecular weight: 30,000, propylene glycol monomethyl ether acetate 30 mass% solution)

XA-2: benzyl methacrylate/methacrylic acid/acrylic acid 2-hydroxyethyl ester=40/30/30 (mass%) copolymer (molecular weight: 30,000, propylene glycol monomethyl ether acetate 30 mass% solution)

XA-3: benzyl methacrylate/methacrylic acid=70/30 (mass%) copolymer (molecular weight: 5,000, propylene glycol monomethyl ether acetate 30 mass% solution)

XA-4: elite UE-3980 (saturated copolyester resin, UNITKA LTD.)

XA-5: DIANAL BR-113 (acrylic resin, mitsubishi Chemical Corporation)

XA-6: PHENOLITE PR-55 (cresol novolak resin, DIC CORPORATION)

XA-7: ZX-412 (fluororesin/Silicone graft resin, T & K TOKA Corporation)

XA-8: LUMIFLON LF200MEK (fluororesin, AGC Inc.)

XB-1：LIGHT ACRYLATE DPE-6A(KYOEISHA CHEMICAL CO.，LTD.)

XC-1：Irgacure OXE02(BASF Japan Ltd.)

XE-2:2, 5-dimercapto-1, 3, 4-thiadiazole (manufactured by Tokyo chemical industry Co., ltd.)

XF-3: 2-naphthalenethiol (manufactured by Tokyo chemical industry Co., ltd.)

XE-4: 2-mercaptobenzimidazole (Tokyo chemical industry Co., ltd.)

XE-5:2, 5-bis (dithiooctyl) -1,3, 4-thiadiazole (manufactured by alfa chemistry Co., ltd.)

XE-6:2, 6-Di-tert-butyl-p-cresol (manufactured by Tokyo chemical industry Co., ltd.)

XE-7: ADEKA STAB AO-30 (ADEKA CO., LTD.,. Manufacturing.)

XE-8: ADEKA STAB PEP-8 (ADEKA CO., LTD.)

XE-9: ADEKA STAB AO-503 (manufactured by ADEKA CO., LTD.)

XE-10: ADEKA STAB LA-52 (ADEKA CO., LTD.,. Manufacturing.)

XF-1: propylene glycol monomethyl ether acetate (Showa Denko K.K.)

XF-2: methyl ethyl ketone (SANKYO chemistry co., ltd.)

[ preparation of composition for Forming thermoplastic resin layer ]

The thermoplastic resin layer-forming composition is prepared by mixing the following compounds.

A-2:42.85 parts by mass

B-5:4.33 parts by mass

B-6:2.31 parts by mass

B-7:0.77 part by mass

E-7:0.03 part by mass

F-1:39.80 parts by mass

F-2:9.51 parts by mass

Compound (B): 0.32 part by mass

Compound (D): 0.08 part by mass

[ preparation of Water-soluble resin layer Forming composition ]

The following compounds were mixed to prepare a composition for forming a water-soluble resin layer.

A-5:3.22 parts by mass

A-6:1.49 parts by mass

E-8:0.0015 part by mass

F-3:38.12 parts by mass

F-4:57.17 parts by mass

[ preparation of composition for Forming photosensitive resin layer ]

By mixing the compounds described in table 2, a composition for forming a photosensitive resin layer was prepared. The unit of the amount of each compound shown in table 2 represents parts by mass.

TABLE 2

Composition for forming photosensitive resin layer	1	2	3	4	5
						A-1	25.4	-	-	25.4	25.4
A-3	-	9.6	-	-	-
						A-4	-	-	9.6	-	-
B-1	4.1	-	-	3.2	3.2
						B-2	2.2	-	-	-	-
B-3	-	-	-	3.1	-
						B-4	-	-	-	-	3.1
C-1	0.25	-	-	0.25	0.25
						C-2	0.04	-	-	0.04	0.04
C-3	-	0.25	-	-	-
						C-4	-	-	0.48	-	-
D-1	0.0175	-	-	0.0175	0.0175
						D-2	0.0011	-	-	0.0011	0.0011
E-1	0.051	-	-	0.051	0.051
						E-2	0.02	-	-	0.02	0.02
E-3	-	0.1	-	-	-
						E-6	0.15	-	-	0.15	0.15
E-7	0.05	0.05	0.05	0.05	0.05
						F-1	39.59	32.00	32.00	39.59	39.59
F-2	26.10	58.00	57.87	26.10	26.10
						F-4	2.00	-	-	2.00	2.00

Abbreviations for compounds used as raw materials for forming the compositions of the layers already described have the following meanings, respectively.

A-1: propylene glycol monomethyl ether acetate solution of copolymer of styrene/methacrylic acid/methyl methacrylate=52/29/19 (mass%) (solid content: 30.0 mass%, mw:70,000, alkali-soluble resin)

A-2: propylene glycol monomethyl ether acetate solution of benzyl methacrylate, methacrylic acid and acrylic acid copolymer (solid content: 30.0% by mass, mw:30,000, acid value: 153 mgKOH/g)

A-3: polymer (A) (resin whose polarity is changed by acid)

A-4: PHENOLITE WR-101 (DIC CORPORATION, resin with phenolic hydroxyl groups)

A-5: KURARAY POVAL PVA-205 (KURARAY CO., LTD., water-soluble resin)

A-6: polyvinylpyrrolidone K-30 (NIPPON SHOKUBIAI CO., LTD., water-soluble resin)

B-1: NK ESTER BPE-500 (SHIN-NAKAMURA CHEMICAL CO, LTD.)

B-2: NK ESTER HD-N (SHIN-NAKAMURA CHEMICAL CO, LTD., polymerizable Compound)

B-3: sartomer SR454 (Arkema S.A., polymeric Compound)

B-4: dimethacrylates (polymerizable compounds) of polyethylene glycol obtained by adding an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol A

B-5: NK ESTER A-DCP (SHIN-NAKAMURA CHEMICAL CO, LTD.) (polymerizable Compound)

B-6:8UX-015A (TAISEI FINE CHEMICAL CO,. LTD.,. Polymeric Compounds)

B-7: aromix TO-2349 (TOAGOSEI co., ltd., polymeric compound)

C-1: B-CIM (2, 2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, KUROGANE KASEI Co., ltd., photopolymerization initiator)

C-2: SB-PI 701 (SANYO TRADING CO., LTD., sensitizer)

C-3: compound CB) (photoacid generator)

C-4:4NT-300 (Toyo Gosei co., ltd, quinone diazide derivatives)

D-1: TDP-G (Kawaguchi Chemical Industry Co., LTD., polymerization inhibitor)

D-2: 1-phenyl-3-pyrazolidinone (FUJIFILM Wako Pure Chemical Corporation, inhibitor)

E-1: colorless crystal violet (Tokyo Chemical Industry co., ltd., hydrogen donor)

E-2: N-phenylcarbamoylmethyl-N-carboxymethylaniline (FUJIFILM Wako Pure Chemical Corporation, hydrogen donor)

E-3: compound (C) (other component)

E-4: compound (D) (pigment B)

E-5: diethylamino-benzenesulfonyl-based ultraviolet absorber (Daito Kagaku Kk, ultraviolet absorber)

E-6:1,2, 4-triazole (Tokyo Chemical Industry co., ltd., heterocyclic compound)

E-7: MEGAFACE F-552 (DIC CORPORATION, surfactant)

E-8: MEGAFACE F-444 (DIC CORPORATION, surfactant)

F-1: methyl ethyl ketone (SANKYO CHEMICAL co., ltd., solvent)

F-2: propylene glycol monomethyl ether acetate (Showa Denko K.K., solvent)

F-3: deionized water (solvent)

F-4: methanol (MITSUBISHI GAS CHEMICAL compass, inc., solvent)

The polymer (A) has the following structure. The composition ratio of the structural units in the following structure represents the mass ratio. The weight average molecular weight of the polymer (A) was 15,000.

[ chemical formula 22]

The compound (B) has the following structure.

[ chemical formula 23]

The compound (C) has the following structure.

[ chemical formula 24]

The compound (D) has the following structure.

[ chemical formula 25]

[ production of transfer Material ]

As a temporary support, a polyethylene terephthalate film (thickness: 16 μm, haze: 0.12%) was prepared. The thermoplastic resin layer-forming composition was applied to the temporary support using a slit nozzle so that the application width became 1.0m and the film thickness after drying became 3.0. Mu.m. The applied thermoplastic resin layer-forming composition was dried at 80 ℃ for 40 seconds to form a thermoplastic resin layer.

The composition for forming a water-soluble resin layer was applied to the thermoplastic resin layer using a slit nozzle so that the application width became 1.0m and the film thickness after drying became 1.2. Mu.m. The coated water-soluble resin layer composition was dried at 80 ℃ for 40 seconds to form a water-soluble resin layer.

The composition for forming a photosensitive resin layer selected according to the description in table 3 was applied to the water-soluble resin layer using a slit nozzle so that the application width became 1.0m and the film thickness after drying became 5.0 μm. The coated photosensitive resin layer-forming composition was dried at 100 ℃ for 2 minutes to form a photosensitive resin layer.

A photosensitive resin layer and a protective film (polypropylene film, thickness: 12 μm) were bonded to each other to prepare a transfer material.

The surface free energy of the photosensitive resin layer was measured by a method based on the above-mentioned method for measuring the surface free energy of the conductive layer. Specifically, the surface free energy was calculated by the Owens and Wendt method from the contact angle of distilled water or diiodomethane with respect to the surface of the photosensitive resin layer exposed by peeling the protective film. The measurement results are shown in Table 3.

[ evaluation ]

The following evaluation was performed using the combination of the transfer material and the laminate selected according to the description in table 3.

(adhesion)

After the protective film was peeled off from the transfer material, the photosensitive resin layer of the transfer material was adhered to the 2 nd surface of the conductive layer at a roll temperature of 100 ℃, a line pressure of 0.8MPa, and a line speed of 3.0 m/min. The sample pieces collected from the obtained laminate were autoclaved at 50℃and 0.5 MPa. After the temporary support was peeled off from the test piece, a transverse cutting test was performed according to "JIS K5600" using a transverse cutting machine (No. 551-AUTO-1, YASUDA SEIKI SEISAKUSHO, LTD.). The adhesion between the conductive layer and the photosensitive resin layer was evaluated based on the residual ratio of the photosensitive resin layer according to the following criteria. In the following references, the higher the residual ratio, the more preferable.

A:90% or more of

B:80% or more and less than 90%

C:70% or more and less than 80%

D: below 70%

(resolution)

According to the method described in the above-described evaluation of adhesion, the photosensitive resin layer of the transfer material was adhered to the 2 nd surface of the conductive layer. A glass mask having lines with a line width of 3 μm to 40 μm and a space pattern (duty ratio=1:1, number of lines in each line width=10) was brought into close contact with a temporary support, and then the photosensitive resin layer was exposed via the temporary support using an exposure machine (M-1S, MIKASA co., LTD). The exposure amount was determined by the following method. After the photosensitive resin layer of the transfer material is adhered to the 2 nd surface of the conductive layer by the above-described method, the photosensitive resin layer is exposed to light through a Stouffer exposure ruler T4105 without peeling off the temporary support. A plurality of samples were prepared by changing the exposure amount, and the exposure amount at which the photosensitive resin layer just disappeared at the 12 th level after development was used as the set exposure amount.

After 1 hour from the start of exposure of the photosensitive resin layer, the temporary support was peeled off. The uncured portion of the photosensitive resin layer was removed by spraying a developing solution (28 ℃ C., 1.0% aqueous potassium carbonate solution) for 30 seconds to the exposed photosensitive resin layer using a shower, and a resin pattern was produced.

Silver nanowires contained in the conductive layer not covered with the resin pattern were removed by spraying an aqueous nitric acid solution (30 c, 40.0 mass%) for 30 seconds to the substrate having the resin pattern using a sprayer.

The resin pattern was removed by spraying a tetramethyl ammonium hydroxide aqueous solution (2.38 mass%) at 40 ℃ to the substrate having the resin pattern using a sprayer, and a conductive pattern was produced.

The line and space in each line width of the conductive pattern were observed, and the line formed by 10 lines which were not peeled off or destroyed was taken as the object, and the minimum line width was taken as the resolution of the conductive pattern. When the lines and spaces are observed, the portions of the silver nanowire layer are visually recognized as line patterns (i.e., conductive patterns) in a dark field observation mode of a metal microscope (MX 50, olympus Corporation). Based on the resolution of the conductive pattern, the resolution was evaluated according to the following criteria. In the following references, finer line and space patterns can be formed, and more preferable.

A: less than 10 mu m

B: more than 10 μm and less than 12 μm

C: more than 12 μm and 20 μm or less

D: exceeding 20 μm

TABLE 3

TABLE 4

< examples 1A to 31A >

The same evaluations as in examples 1 to 31 were performed except that the temporary support and the protective film were changed to the following combinations in the production of the transfer material. The evaluation results of examples 1A to 31A were the same as those of examples 1 to 31, respectively.

Temporary support: cosmosine A4160 (thickness: 50 μm) (TOYOBO CO., LTD.)

Protective film: alpha E-210F (thickness: 50 μm) (Oji F-Tex Co., ltd.)

< examples 1B to 31B >)

The same evaluations as in examples 1 to 31 were performed except that the temporary support and the protective film were changed to the following combinations in the production of the transfer material. The evaluation results of examples 1B to 31B were the same as those of examples 1 to 31, respectively.

Temporary support: cosmosine A4360 (thickness: 38 μm) (TOYOBO CO., LTD.)

Protective film: alpha FG-201 (thickness: 30 μm) (Oji F-Tex Co., ltd.)

< examples 1C to 31C >

The same evaluations as in examples 1 to 31 were performed except that the temporary support and the protective film were changed to the following combinations in the production of the transfer material. The evaluation results of examples 1C to 31C were the same as those of examples 1 to 31, respectively.

Temporary support: lumirror #38-U48 (thickness: 38 μm) (TORAY INDUSTRIES, INC.)

Protective film: alpha E-210F (thickness: 50 μm) ((Oji F-Tex Co., ltd.)

< example 1D-example 31D >

The same evaluations as in examples 1 to 31 were performed except that the temporary support and the protective film were changed to the following combinations in the production of the transfer material. The evaluation results of examples 1D to 31D were the same as those of examples 1 to 31, respectively.

Temporary support: lumirror #75-U34 (thickness: 75 μm) (TORAY INDUSTRIES, INC.)

Protective film: alpha FG-201 (thickness: 30 μm) (Oji F-Tex Co., ltd.)

< example 1E to example 31E >

The same evaluations as in examples 1 to 31 were performed except that the temporary support and the protective film were changed to the following combinations in the production of the transfer material. The evaluation results of examples 1E to 31E are the same as those of examples 1 to 31, respectively.

Temporary support: lumirror16FB40 (thickness: 16 μm) (TORAY INDUSTRIES, INC.)

Protective film: alpha E-210F (thickness: 50 μm) (Oji F-Tex Co., ltd.)

< example 1F-example 31F >

The same evaluations as in examples 1 to 31 were performed except that the temporary support and the protective film were changed to the following combinations in the production of the transfer material. The evaluation results of examples 1F to 31F were the same as those of examples 1 to 31, respectively.

Temporary support: lumirror16FB40 (thickness: 16 μm) (TORAY INDUSTRIES, INC.)

Protective film: alpha FG-201 (thickness: 30 μm) (Oji F-Tex Co., ltd.)

< example 1G-example 31G >

The same evaluations as in examples 1 to 31 were performed except that the temporary support and the protective film were changed to the following combinations in the production of the transfer material. The evaluation results of examples 1G to 31G are the same as those of examples 1 to 31, respectively.

Temporary support: lumirror16KS40 (thickness: 16 μm) (TORAY INDUSTRIES, INC.)

Protective film: alpha FG-201 (thickness: 30 μm) (Oji F-Tex Co., ltd.)

Symbol description

10-substrate, 20-conductive layer, 20 a-conductive layer 2 nd, 21-conductive layer (A), 21 a-conductive layer (A) 2 nd, 30-photosensitive resin layer, 30 a-photosensitive resin layer 3 rd.

Claims (14)

1. A method for manufacturing a resin pattern, comprising, in order:

a step of preparing a laminate including a substrate and a conductive layer having a 1 st surface facing the substrate and a 2 nd surface on the opposite side of the 1 st surface;

a step of forming a photosensitive resin layer on the 2 nd surface of the conductive layer, the photosensitive resin layer having a 3 rd surface facing the conductive layer and a 4 th surface on the opposite side of the 3 rd surface;

a step of exposing the photosensitive resin layer to a pattern; a kind of electronic device with high-pressure air-conditioning system

A step of developing the photosensitive resin layer to form a resin pattern,

the conductive layer contains a metal nanomaterial and a resin,

the surface free energy γs1 of the 2 nd surface of the conductive layer and the surface free energy γr of the 3 rd surface of the photosensitive resin layer satisfy the relationship of |γs1- γr|less than or equal to 12.

2. The method for producing a resin pattern according to claim 1, wherein,

the surface free energy gamma s1 and the surface free energy gamma r meet the relation of |gamma s 1-gamma r| less than or equal to 3.

3. The method for producing a resin pattern according to claim 1, wherein,

the resin contains an acrylic resin.

4. The method for producing a resin pattern according to claim 1, wherein,

the conductive layer is formed by bringing a solution containing an organic substance and a solvent into contact with a conductive layer a containing the metal nanomaterial and a resin a.

5. The method for producing a resin pattern according to claim 4, wherein,

the resin A contains cellulose derivatives.

6. The method for producing a resin pattern according to claim 1, wherein,

the metal nano material is silver nano wire.

7. The method for producing a resin pattern according to claim 1, wherein,

the photosensitive resin layer contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

8. The method for producing a resin pattern according to claim 1, wherein,

the photosensitive resin layer contains a resin whose polarity is changed by an acid and a photoacid generator.

9. The method for producing a resin pattern according to claim 1, wherein,

the photosensitive resin layer contains a resin having a phenolic hydroxyl group and a quinone diazide derivative.

10. The method for producing a resin pattern according to claim 1, wherein,

the photosensitive resin layer contains a heterocyclic compound.

11. The method for producing a resin pattern according to claim 1, wherein,

the step of forming the photosensitive resin layer includes: a step of preparing a transfer material including a temporary support and the photosensitive resin layer; and adhering the photosensitive resin layer of the transfer material to the conductive layer.

12. A method for manufacturing a conductive pattern, which comprises the following steps in order:

a step of forming a resin pattern by the method for producing a resin pattern according to any one of claims 1 to 11;

a step of etching the conductive layer using the resin pattern as a mask to form a conductive pattern; a kind of electronic device with high-pressure air-conditioning system

And removing the resin pattern.

13. A laminate, comprising:

a substrate; a kind of electronic device with high-pressure air-conditioning system

A conductive layer having a 1 st surface facing the substrate and a 2 nd surface on the opposite side of the 1 st surface,

The conductive layer contains a metal nanomaterial and a resin,

the surface free energy γs1 of the 2 nd surface of the conductive layer is 30mJ/m ² ～50mJ/m ² 。

14. A laminate, comprising:

a substrate; a kind of electronic device with high-pressure air-conditioning system

A conductive layer having a 1 st surface facing the substrate and a 2 nd surface on the opposite side of the 1 st surface,

the conductive layer contains a metal nanomaterial and a resin,

the contact angle of distilled water with the 2 nd surface of the conductive layer is 50 DEG to 85 deg.

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