WO2020105457A1

WO2020105457A1 - Transfer material, resin pattern production method, circuit wiring production method, and touch panel production method

Info

Publication number: WO2020105457A1
Application number: PCT/JP2019/043695
Authority: WO
Inventors: 洋行海鉾; 藤本　進二; 一真両角
Original assignee: 富士フイルム株式会社
Priority date: 2018-11-20
Filing date: 2019-11-07
Publication date: 2020-05-28
Also published as: CN113056373A; JPWO2020105457A1

Abstract

The invention provides a transfer material having a temporary support, an intermediate layer containing a water-soluble resin, and a positive type photosensitive resin layer, in this order, wherein the intermediate layer contains a surfactant having a fluorine atom; the invention also provides a resin pattern production method, a circuit wiring production method, and a touch panel production method, which use the transfer material.

Description

Transfer material, resin pattern manufacturing method, circuit wiring manufacturing method, and touch panel manufacturing method

The present disclosure relates to a transfer material, a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method.

2. Description of the Related Art In a display device (organic electroluminescence (EL) display device, liquid crystal display device, etc.) equipped with a touch panel such as a capacitance type input device, an electrode pattern corresponding to a sensor of a visual recognition part, a wiring of a peripheral wiring part and an extraction wiring part A conductive layer pattern such as is provided inside the touch panel.
In general, a patterned layer is formed by a small number of steps for obtaining a required pattern shape. Therefore, a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material. On the other hand, a method of developing after exposing through a mask having a desired pattern is widely used.

Further, as the conventional photosensitive resin composition or transfer material, those described in Patent Document 1 or 2 are known.
Patent Document 1 has a temporary support, an intermediate layer, and a photosensitive resin composition layer in this order, and the photosensitive resin composition layer has an acid group protected by an acid-decomposable group. Containing a polymer having a structural unit, and a photoacid generator, the intermediate layer is water-soluble or alkali-soluble, and a structural unit having a phenolic hydroxyl group or an alcoholic hydroxyl group not directly linked to the main chain Photosensitive transfer materials containing Resin C containing are described.

In Patent Document 2, at least one transfer layer is provided on a temporary support, and the maximum peeling force when peeling the temporary support is 0.98 to 5.39 mN / cm in a 180 ° peel method. Certain transfer laminates are described.

Patent Document 1: International Publication No. 2018/179640 Patent Document 2: Japanese Patent Application Laid-Open No. 2009-73022

The problem to be solved by one embodiment of the present invention is to provide a transfer material having less streaks on the surface to be transferred.
Further, another problem to be solved by another embodiment of the present invention is to provide a method for manufacturing a resin pattern using the above transfer material, a method for manufacturing circuit wiring, and a method for manufacturing a touch panel.

Means for solving the above problems include the following aspects.
<1> A transfer material having a temporary support, an intermediate layer containing a water-soluble resin, and a positive photosensitive resin layer in this order, and the intermediate layer containing a surfactant having a fluorine atom.
<2> The transfer material according to <1>, wherein the surfactant contains a compound having a molecular weight of 700 or more.
<3> The transfer material according to <1> or <2>, wherein the surfactant has a solubility of 1 g or more in 100 g of water at 25 ° C.
<4> The content of the surfactant according to any one of <1> to <3>, which is 0.1% by mass to 1.0% by mass with respect to the total mass of the intermediate layer. Transfer material.
<5> The transfer material according to any one of <1> to <4>, wherein the surfactant is a surfactant having a fluoroalkyl group and an alkyleneoxy group.
<6> The transfer material according to any one of <1> to <5>, wherein the surfactant is a surfactant having a perfluoroalkyl group and a polyalkyleneoxy group.
<7> Any one of <1> to <6>, wherein the content of the polymer component in the positive photosensitive resin layer is 75% by mass or more based on the total mass of the positive photosensitive resin layer. The transfer material described in 1.
<8> Any one of <1> to <7>, in which the positive photosensitive resin layer contains a polymer containing a structural unit having an acid group protected by an acid-decomposable group, and a photo-acid generator. The transfer material according to one.
<9> The transfer material according to <8>, wherein the structural unit having an acid group protected by an acid-decomposable group is a structural unit represented by any one of the following formulas A1 to A3.

In formula A1, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹¹ and R ¹² is an alkyl group or an aryl group, and R ¹³ is an alkyl group or It represents an aryl group, R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, R ¹⁴ is a hydrogen atom or a methyl group, and X ¹ is a single bond or a divalent linking group. R ¹⁵ represents a substituent, and n represents an integer of 0 to 4.
In formula A2, R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ²¹ and R ²² is an alkyl group or an aryl group, and R ²³ is an alkyl group or It represents an aryl group, and R ²¹ or R ²² and R ²³ may be linked to form a cyclic ether, and R ²⁴ is independently a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, It represents 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 formula A3, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group or It represents an aryl group, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or a divalent linking group. Represents.

<10> A step of bringing the outermost layer on the side having the positive photosensitive resin layer into contact with the substrate and adhering to the temporary support in the transfer material according to any one of <1> to <9>. A method of manufacturing a resin pattern, comprising: a step of pattern-exposing the positive photosensitive resin layer, and a step of developing the exposed positive photosensitive resin layer to form a resin pattern, in this order.
<11> The outermost layer on the side having the positive photosensitive resin layer with respect to the temporary support in the transfer material according to any one of <1> to <9> is brought into contact with a substrate having a conductive layer. And a step of patterning the positive photosensitive resin layer, a step of developing the exposed positive photosensitive resin layer to form a resin pattern, and the resin pattern are arranged. And a step of etching the conductive layer in a non-existing region in this order.
<12> The outermost layer on the side having the positive photosensitive resin layer with respect to the temporary support in the transfer material according to any one of <1> to <9> is brought into contact with a substrate having a conductive layer. And a step of patterning the positive photosensitive resin layer, a step of developing the exposed positive photosensitive resin layer to form a resin pattern, and the resin pattern are arranged. And a step of etching the conductive layer in a non-existing region in this order.

According to one embodiment of the present invention, it is possible to provide a transfer material having few streaks on the surface to be transferred.
Further, according to another embodiment of the present invention, it is possible to provide a method for manufacturing a resin pattern, a method for manufacturing circuit wiring, and a method for manufacturing a touch panel, which use the transfer material.

It is a schematic diagram showing an example of layer composition of a transfer material concerning this indication. It is a schematic diagram showing pattern A. It is a schematic diagram showing pattern B.

The contents of the present disclosure will be described below. The description will be made with reference to the accompanying drawings, but the reference numerals may be omitted.
Further, in the present specification, the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
Moreover, in this specification, "(meth) acryl" represents both acryl and methacryl, or either, and "(meth) acrylate" represents both an acrylate and a methacrylate.
Further, in the present specification, the amount of each component in the composition is the sum of the corresponding plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the composition. Means quantity.
In the present specification, the term “process” is included not only in an independent process but also in the case where the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
In the description of the group (atom group) in the present specification, the notation in which substitution and non-substitution are not included includes not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, the term “exposure” as used herein includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. In addition, as the light used for the exposure, generally, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), active rays (active energy rays) such as X-rays and electron rays are used. Can be mentioned.
In addition, the chemical structural formula in the present specification may be described as a simplified structural formula in which a hydrogen atom is omitted.
In the present disclosure, “mass%” and “weight%” have the same meaning, and “mass part” and “weight part” have the same meaning.
Further, in the present disclosure, a combination of two or more preferable aspects is a more preferable aspect.
In addition, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both manufactured by Tosoh Corporation) unless otherwise specified. The gel permeation chromatography (GPC) analyzer was used to detect the solvent THF (tetrahydrofuran) with a differential refractometer, and the molecular weight was calculated using polystyrene as a standard substance.

(Transfer material)
The transfer material (also referred to as “photosensitive transfer material”) according to the present disclosure includes a temporary support, an intermediate layer containing a water-soluble resin, and a positive photosensitive resin layer (hereinafter, also simply referred to as “photosensitive resin layer”). And) in this order, and the intermediate layer contains a surfactant having a fluorine atom.
The transfer material according to the present disclosure is a positive photosensitive transfer material.

When manufacturing the intermediate layer and the positive type photosensitive resin layer, the positive type photosensitive resin layer is a hard layer containing a resin as a main component and has low fluidity. , Shape defects such as stripes which are influenced by the shape of the intermediate layer when the intermediate layer is formed reflect similar shape defects to the positive photosensitive resin layer, and further When the layer of No. 1 is further formed, similar shape defects may be reflected up to that layer. Thus, in the transfer material having the intermediate layer and the positive photosensitive resin layer, the surface to be transferred is The present inventors have found that there is a problem that streaks occur in the above.
On the other hand, the negative photosensitive resin layer described in Patent Document 2 and the like is a layer containing a polymerizable compound and has high fluidity, and thus streaks and the like generated during the formation of the intermediate layer during the formation of the negative photosensitive resin layer. The influence of the shape defect is not reflected, and the negative photosensitive resin layer is flattened, so that the problem of streaks on the transferred surface does not occur as described above.
Therefore, the problem of reducing streaks on the transferred surface is a problem peculiar to the positive photosensitive resin layer.
The “transfer surface” is also referred to as a “transfer surface”, and for example, if the transfer material has a temporary support, an intermediate layer, and a positive photosensitive resin layer in this order, This is the surface on the positive photosensitive resin layer side.

As a result of intensive studies, the inventors of the present invention have found that the transfer material having the above-mentioned structure can provide a transfer material having few streaks on the surface to be transferred.
Although the detailed mechanism of expressing the above effect is unknown, a temporary support, an intermediate layer, and a positive photosensitive resin layer in this order, the intermediate layer contains a surfactant having a fluorine atom, Generation of streaks on the surface of the intermediate layer is suppressed, deterioration of the surface shape of the positive photosensitive resin layer due to the generation of streaks is suppressed, and a transfer material having few streaks on the surface to be transferred is obtained. It is estimated to be.
It is presumed that the above-mentioned generation of streaks is caused by convection of the intermediate layer forming layer composition during the formation of the intermediate layer and uneven volatilization of the solvent contained in the intermediate layer forming layer composition.

In addition, as described above, the positive photosensitive resin layer is a hard layer containing a resin as a main component and has low fluidity, so that the influence of the stripes generated in the intermediate layer is reflected on the transfer surface, and Occurs. Generation of the streak can be suppressed by including the surfactant having a fluorine atom in the intermediate layer. Since the generation of the streaks is suppressed, at the time of transfer, at the bonded portion on the transfer surface, it is possible to suppress bubbles from entering the streaks, excellent adhesion on the transfer surface, and a transfer material as an etching resist. When the above is used, there are few defects in the resin pattern shape derived from the above-mentioned streaks and bubbles, and the accompanying defects such as disconnection of wiring which is an etching pattern and unnecessary coupling and contact (short).
Therefore, the transfer material according to the present disclosure has excellent adhesiveness in transfer due to the above-described configuration, and has few wiring defects when the transfer material is used as the etching resist.

Hereinafter, the transfer material according to the present disclosure will be described in detail.

<Middle layer>
The transfer material according to the present disclosure has an intermediate layer.
The intermediate layer contains a fluorine atom-containing surfactant and a water-soluble resin, and preferably contains a fluorine atom-containing surfactant, a water-soluble resin, and a dye described below.

[Surfactant having a fluorine atom]
The intermediate layer contains a surfactant having a fluorine atom.
Examples of the surfactant having a fluorine atom include compounds having a group having a fluorine atom and a hydrophilic group.
The surfactant having a fluorine atom may have only one group having a fluorine atom or may have two or more groups.
The surfactant having a fluorine atom may have only one hydrophilic group or two or more hydrophilic groups.

From the viewpoint of suppressing the generation of streaks, the surfactant having a fluorine atom preferably has a fluoroalkyl group or a fluoroaryl group as a group having a fluorine atom, more preferably a fluoroalkyl group, and a perfluoroalkyl group. It is particularly preferable to have a group.
From the viewpoint of suppressing the generation of streaks, the perfluoroalkyl group is preferably a perfluoroalkyl group having 4 or more carbon atoms, more preferably a perfluoroalkyl group having 4 to 18 carbon atoms, A perfluoroalkyl group having 4 to 12 carbon atoms is more preferable, and a perfluoroalkyl group having 4 to 6 carbon atoms is particularly preferable.

The surfactant having a fluorine atom is an ionic surfactant having a fluorine atom or a nonionic surfactant having a fluorine atom, from the viewpoints of suppressing the generation of streaks and the adhesion on the transfer surface during transfer. Is more preferable, an anionic surfactant having a fluorine atom or a nonionic surfactant having a fluorine atom is more preferable, and a nonionic surfactant having a fluorine atom is particularly preferable.
The ionic hydrophilic group, hydrophilicity, suppression of streak generation, and from the viewpoint of adhesion on the transfer surface at the time of transfer, preferably an acid group, a carboxy group, a sulfo group, a phosphonic acid group, Alternatively, a phosphoric acid group is more preferable, and a phosphoric acid group is particularly preferable.
As the nonionic hydrophilic group, hydrophilicity, suppression of streak generation, and from the viewpoint of adhesion on the transfer surface at the time of transfer, an alkyleneoxy group or a hydroxy group is preferable, and an alkyleneoxy group is More preferably, a polyalkyleneoxy group is particularly preferable.
The surfactant having a fluorine atom is at least selected from the group consisting of an acid group and an alkyleneoxy group as the hydrophilic group, from the viewpoint of suppressing the generation of streaks, and the adhesion on the transfer surface at the time of transfer. It preferably has one group, more preferably has an alkyleneoxy group, and particularly preferably has a polyalkyleneoxy group.
The alkyleneoxy group is preferably an ethyleneoxy group or a propyleneoxy group.
The polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, or a group formed by bonding one or more ethyleneoxy groups and one or more propyleneoxy groups.

The surfactant having a fluorine atom is preferably a surfactant having a fluoroalkyl group and an alkyleneoxy group, from the viewpoint of suppressing the generation of streaks and the adhesion on the transfer surface at the time of transfer, and perfluoro A surfactant having an alkyl group and a polyalkyleneoxy group is more preferable, and a surfactant having a perfluoroalkyl group having 4 or more carbon atoms and a polyalkyleneoxy group is particularly preferable.

The intermediate layer may contain one type of surfactant having a fluorine atom, or two or more types thereof.
The surfactant having a fluorine atom in the intermediate layer preferably contains a compound having a molecular weight of 500 or more, and a compound having a molecular weight of 700 or more, from the viewpoint of suppressing the generation of streaks and the adhesion between the photosensitive resin layer and the intermediate layer. Is more preferable, and it is particularly preferable to include a compound having a molecular weight of 1,000 or more and 10,000 or less. Further, the surfactant having a fluorine atom is preferably a compound having a weight average molecular weight (Mw) of 20,000 or less, and a weight average molecular weight of 10,000 or less, from the viewpoint of adhesion on the transfer surface during transfer. More preferably, it is a compound.

The solubility of the fluorine atom-containing surfactant in 100 g of water at 25 ° C. is preferably 0.5 g or more, from the viewpoint of suppressing streak generation and suppressing the precipitation of the fluorine atom-containing surfactant, 1 g or more Is more preferable.
As an example of the surfactant having a fluorine atom, each series of Megafac (manufactured by DIC Corporation) can be preferably mentioned.

The content of the fluorine atom-containing surfactant is from 0.05% by mass to 2% with respect to the total mass of the intermediate layer from the viewpoints of suppressing the generation of streaks and the adhesiveness between the photosensitive resin layer and the intermediate layer. The content is preferably 0.0% by mass, more preferably 0.1% by mass to 1.0% by mass, and particularly preferably 0.2% by mass to 0.4% by mass.

[Water-soluble resin]
The intermediate layer contains a water-soluble resin.
Examples of the water-soluble resin include cellulose resins, polyvinyl alcohol resins, polyvinylpyrrolidone resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and resins such as copolymers thereof. Is mentioned. Of these, a cellulose resin is preferable, and at least one resin selected from the group consisting of hydroxypropyl cellulose and hydroxypropylmethyl cellulose is more preferable.

As the water-soluble resin, a water-soluble or alkali-soluble acrylic resin is preferably mentioned. In the present disclosure, “water-soluble” means that the solubility in 100 g of water having a pH of 7.0 at 22 ° C. is 0.1 g or more, and “alkali-soluble” means sodium carbonate at 22 ° C. It means that the solubility in 100 g of a 1 mass% aqueous solution is 0.1 g or more.
The term "water-soluble or alkali-soluble" may be either water-soluble or alkali-soluble, or water-soluble and alkali-soluble.
The solubility of the water-soluble resin in 100 g of water having a pH of 7.0 at 22 ° C. is preferably 1 g or more, and more preferably 5 g or more.
From the viewpoint of water solubility or alkali solubility, the water-soluble or alkali-soluble acrylic resin preferably has a hydrophilic group, and more preferably has a structural unit having a hydrophilic group.
Examples of the hydrophilic group include an acid group which may form a salt, a hydroxy group, a polyalkyleneoxy group, an amide group, and a basic group which may form a salt, and the like, and from the viewpoint of adhesion, It is preferable to have at least an acid group or a hydroxy group that may form a salt.

The intermediate layer may contain one type of water-soluble resin or two or more types.
The content of the water-soluble resin, the shape of the obtained pattern, the adhesion on the transfer surface at the time of transfer, and from the viewpoint of the adhesion between the photosensitive resin layer and the intermediate layer, relative to the total mass of the intermediate layer, It is preferably 20% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass.

[Dye]
From the viewpoint of easy confirmation of the exposure pattern, the intermediate layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development, and a dye (simply referred to as “dye It is also referred to as ".".
Dyes "maximum absorption wavelength is changed by acid, base or radical" means that the dye in the colored state is decolored by acid, base or radical, the dye in the decolored state is colored by acid, base or radical. And the aspect in which the dye in the coloring state changes to the coloring state of another hue.
Specifically, the dye may be a compound that changes from the decolored state to a color upon exposure to light, or a compound that changes from the decolored state to a color upon exposure to light. In this case, a dye whose color development or decolorization state is changed by introducing an acid, a base or a radical into the intermediate layer by exposure may be used, and a property in the system by introducing an acid, a base or a radical ( For example, it may be a dye whose color-developed or decolored state changes when pH) changes. Further, it may be a dye in which an acid, a base, or a radical is directly given as a stimulus to directly change the state of color development or decolorization without exposure.
Among them, the dye may be a compound that develops color upon exposure to light or a compound that disappears upon exposure to light, but from the viewpoint of visibility, it is preferable that it is a compound that disappears upon exposure to light. It is more preferable to use a latent dye that is decolorized by the acid generated from the dye, that is, a pH-sensitive dye that is decolorized by changing the pH due to the generation of acid.

It can be confirmed that the dye is a pH-sensitive dye by the following method.
0.1 g of the dye is dissolved in 100 mL of a mixed solution of ethanol and water (ethanol / water = 1/2 (mass ratio)), and 0.1 mol / L (1N) aqueous hydrochloric acid solution is added to adjust pH = 1. Titrate with 0.01 mol / L (0.01 N) sodium hydroxide aqueous solution to confirm the color change and the pH at which the color change appears. The pH is a value measured at 25 ° C. using a pH meter (model number: HM-31, manufactured by Toa DKK Co., Ltd.).

The maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development of the dye is preferably 550 nm or more, more preferably 550 nm or more and 700 nm or less, and further preferably 550 nm or more and 650 nm or less from the viewpoint of visibility. preferable.
Further, the dye may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development, or may have two or more maximum absorption wavelengths. When the dye has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm at the time of color development, the maximum absorption wavelength having the largest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.
The method for measuring the maximum absorption wavelength in the present disclosure is to measure a transmission spectrum in the wavelength range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) at 25 ° C. in an atmosphere of air. , The wavelength at which the light intensity becomes minimum (maximum absorption wavelength) shall be measured.

Examples of dyes that develop color upon exposure include leuco compounds.
Examples of dyes that are decolorized by exposure include leuco compounds, diphenylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.
Among them, leuco compounds are preferable as the dye from the viewpoint of visibility.
Examples of the leuco compound include triarylmethane-based (eg, triphenylmethane-based), spiropyran-based, fluoran-based, diphenylmethane-based, rhodamine lactam-based, indolylphthalide-based, leucoauramine-based leuco compounds. Of these, leuco compounds having a triarylmethane skeleton (triarylmethane dyes) are preferable, and triphenylmethane dyes are more preferable.
Further, as the leuco compound, from the viewpoint of visibility, a lactone ring, a sultin ring, or a sultone ring is preferable, and a lactone ring, a sultin ring, or a sultone ring that is opened or closed is preferable, and a sultone ring is used. It is more preferable to use a leuco compound having a sultone ring that is closed and decolorized.

The dye is preferably a water-soluble compound for the purpose of preventing defects due to the precipitation of the dye.
The solubility of the dye in 100 g of water having a pH of 7.0 at 22 ° C. is preferably 1 g or more, more preferably 5 g or more.

The intermediate layer may contain one kind of dye or two or more kinds of dye.
From the viewpoint of visibility, the content of the dye in the intermediate layer is preferably 0.01% by mass to 10% by mass, and is 0.1% by mass to 8% by mass, based on the total mass of the intermediate layer. It is more preferably 0.5% by mass to 5% by mass, further preferably 1.0% by mass to 3.0% by mass.

[Other surfactants]
The intermediate layer may contain a surfactant other than the surfactant having a fluorine atom.
As the other surfactant, any of anionic, cationic, nonionic (nonionic) and amphoteric surfactants can be used, and known surfactants can be used.
The content of the other surfactant in the intermediate layer is preferably smaller than the content of the fluorine atom-containing surfactant from the viewpoint of suppressing the generation of streaks.
In the case of containing other surfactant, the content of the other surfactant is 0 relative to the total mass of the intermediate layer from the viewpoint of suppressing the generation of streaks and the adhesion on the transfer surface at the time of transfer. It is preferably 0.01% by mass or more and less than 2.0% by mass.

[Inorganic filler]
The intermediate layer can include an inorganic filler. The inorganic filler in the present disclosure is not particularly limited. Examples thereof include silica particles, aluminum oxide particles and zirconium oxide particles, and silica particles are more preferable. From the viewpoint of transparency, particles having a small particle size are preferable, and particles having an average particle size of 100 nm or less are more preferable. For example, if it is a commercially available product, Snowtex (registered trademark) is preferably used.

The volume fraction of the particles in the intermediate layer (volume ratio of the particles in the intermediate layer) is 5% to 90% with respect to the total volume of the intermediate layer from the viewpoint of adhesion between the intermediate layer and the photosensitive layer. It is preferably 10% to 80%, more preferably 15% to 70%, particularly preferably 20% to 60%.
As will be described later, when the number of intermediate layers is two, the volume fraction of the particles in all the intermediate layers (volume ratio of particles in the intermediate layer) is from the viewpoint of adhesion between the intermediate layer and the photosensitive layer. The total volume of the intermediate layer is preferably 2% to 90%, more preferably 3% to 80%, further preferably 5% to 20%, and 10% to 20%. It is particularly preferable that

[PH adjuster]
The intermediate layer can include a pH adjuster. By including the pH adjusting agent, the coloring state or the decoloring state of the dye in the intermediate layer can be maintained more stably, and the adhesiveness is further improved.
The pH adjusting agent in the present disclosure is not particularly limited. Examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, organic amines, organic ammonium salts and the like. Sodium hydroxide is preferred from the viewpoint of water solubility. From the viewpoint of the adhesiveness between the photosensitive resin layer and the intermediate layer, organic ammonium salts are preferable.
Examples of the organic ammonium salt include a primary ammonium salt, a secondary ammonium salt, a tertiary ammonium salt, and a quaternary ammonium salt, and a quaternary ammonium salt is preferable.
Examples of the quaternary ammonium salt include tetraalkylammonium hydroxide which may have a substituent, and specific examples thereof include tetramethylammonium hydroxide, triethylmethylammonium hydroxide, tetraethylammonium hydroxide, Examples include tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, hexadecyltrimethylammonium hydroxide, choline, benzyltrimethylammonium, benzyltriethylammonium, tris (2-hydroxyethyl) methylammonium hydroxide, etc. .
Among them, tetraalkylammonium hydroxide having an alkyl group having 1 to 30 carbon atoms (preferably 10 to 30 carbon atoms, more preferably 10 to 25 carbon atoms) is more preferable. When it has a substituent, examples of the substituent include an aryl group having 6 to 12 carbon atoms (for example, a phenyl group), a hydroxy group and the like.

[Average thickness of intermediate layer]
The average thickness of the intermediate layer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and more preferably 0.3 μm, from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer and pattern formability. ˜2 μm is particularly preferred.
The average thickness of the intermediate layer is preferably thinner than the average thickness of the photosensitive resin layer.

The intermediate layer may have two or more layers.
When the intermediate layer has two or more layers, the average thickness of each layer is not particularly limited as long as it is within the above range, but of the two or more layers in the intermediate layer, the layer closest to the photosensitive resin layer. The average thickness of is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and more preferably 0.3 μm to 2 μm from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formability. Particularly preferred.
In the method of measuring the average thickness of each layer in the present disclosure, the cross section in the direction perpendicular to the surface direction of the transfer material is observed and measured by a scanning electron microscope (SEM). The average thickness is the average value obtained by measuring the thickness at 10 or more points.

[Method of forming intermediate layer]
The intermediate layer in the present disclosure can be formed by adjusting, coating and drying an intermediate layer-forming composition containing components necessary for forming the intermediate layer and a water-soluble solvent. It is possible to prepare a composition for forming an intermediate layer for forming an intermediate layer by mixing the respective components and a water-soluble solvent in a predetermined ratio and by an arbitrary method and stirring and dissolving. For example, it is possible to prepare a composition by dissolving each component in a solvent in advance and then mixing the obtained solutions in a predetermined ratio. The composition prepared as described above can also be used after being filtered using a filter having a pore size of 3.0 μm or the like.

The intermediate layer can be formed on the temporary support by applying the intermediate layer forming composition to the temporary support and drying the composition. The coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, inkjet coating and the like.

-Intermediate layer forming composition-
The intermediate layer forming composition preferably contains a component contained in the intermediate layer and a water-soluble solvent. A water-soluble solvent is contained in each component to adjust the viscosity, and the intermediate layer can be suitably formed by coating and drying.
Examples of the water-soluble solvent include water and alcohol compounds having 1 to 6 carbon atoms, and water is preferable. Examples of the alcohol compound having 1 to 6 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol and n-hexanol, which are composed of methanol, ethanol, n-propanol and isopropanol. At least one selected from the group is preferable.

<Photosensitive resin layer>
The transfer material according to the present disclosure has a photosensitive resin layer.
The photosensitive resin layer in the present disclosure is a positive photosensitive resin layer, and a known positive photosensitive resin layer can be used. Further, the photosensitive resin layer used in the present disclosure is, from the viewpoint of sensitivity and resolution, an acid-decomposable resin, that is, a polymer having a structural unit having an acid group protected by an acid-decomposable group, and a photoacid generator. It is preferable that the chemical amplification positive type photosensitive resin layer contains a photo-acid generator and a polymer having a structural unit having an acid group protected by an acid-decomposable group.
The photo-acid generators such as onium salts and oxime sulfonate compounds described below have an acid generated in response to actinic radiation (actinic rays) as a catalyst for deprotection of the protected acid group in the polymer. Since it acts, the acid generated by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, which is a large value such as 10 to the power of so-called chemical amplification. As a result, high sensitivity is obtained.
On the other hand, when a quinonediazide compound is used as a photoacid generator sensitive to actinic rays, a carboxy group is produced by a sequential photochemical reaction, but its quantum yield is always 1 or less, which is not a chemical amplification type.

[Polymer A1 having a structural unit having an acid group protected by an acid-decomposable group]
The positive photosensitive resin layer contains a polymer (also simply referred to as "polymer A1") having a structural unit (also referred to as "structural unit A") having an acid group protected by an acid-decomposable group. Is preferred.
In addition to the polymer A1 having the structural unit A, the positive photosensitive resin layer may contain another polymer. In the present disclosure, the polymer A1 having the structural unit A and other polymers are collectively referred to as a “polymer component”.
In the polymer A1, the acid group protected by the acid-decomposable group in the polymer A1 undergoes a deprotection reaction to become an acid group by the action of a catalytic amount of an acid substance such as an acid generated by exposure. This acid group enables dissolution in the developer.

The polymer A1 is preferably an addition polymerization type resin, and more preferably a polymer having a structural unit derived from (meth) acrylic acid or its ester. In addition, you may have a structural unit other than the structural unit derived from (meth) acrylic acid or its ester, for example, the structural unit derived from a styrene compound, the structural unit derived from a vinyl compound, etc.
Hereinafter, preferred embodiments of the structural unit A will be described.

-Structural unit A-
The polymer component preferably contains a polymer A1 having a structural unit A having an acid group protected by an acid-decomposable group. When the photosensitive resin layer contains the polymer A1 having the structural unit A, it is possible to obtain a chemically amplified positive photosensitive resin layer having extremely high sensitivity.
The polymer A1 contained in the positive photosensitive resin layer may be only one kind or two or more kinds.
As the acid group and the acid-decomposable group in the present disclosure, known groups can be used and are not particularly limited. Preferred specific acid groups include a carboxy group and a phenolic hydroxyl group (also referred to as "phenolic hydroxy group"). The acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal-type functional group such as a 1-alkoxyalkyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group) or an acid-decomposable group. A difficult group (for example, a tertiary alkyl group such as a tert-butyl group, a tertiary alkyloxycarbonyl group such as a tert-butyloxycarbonyl group) can be used.
Among these, the acid-decomposable group is preferably a group having a structure protected in the form of acetal.
Further, the acid-decomposable group is preferably an acid-decomposable group having a molecular weight of 300 or less from the viewpoint of suppressing variation in the line width of the conductive wiring when applied to the formation of a conductive pattern.

The structural unit A having an acid group protected by an acid-decomposable group is preferably a structural unit represented by any of the following formulas A1 to A3 from the viewpoint of sensitivity and resolution.

In formula A1, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹¹ and R ¹² is an alkyl group or an aryl group, and R ¹³ is an alkyl group or an aryl group. R ¹¹ or R ¹² and R ¹³ may combine to form a cyclic ether, R ¹⁴ represents a hydrogen atom or a methyl group, and 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 formula A2, R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ²¹ and R ²² is an alkyl group or an aryl group, and R ²³ is an alkyl group or an aryl group. And R ²¹ or R ²² and R ²³ may be linked to each other to form a cyclic ether, and R ²⁴ is independently a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group or an aryl group. Represents 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 formula A3, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group or an aryl group. R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or a divalent linking group. ..

The acid group protected by the acid-decomposable group is preferably a carboxy group protected by an acid-decomposable group, which is a structure that protects in the form of acetal, from the viewpoint of acid decomposition rate and sensitivity.

In formula A3, when R ³¹ or R ³² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ³¹ or R ³² is an aryl group, a phenyl group is preferred. Each of R ³¹ and R ³² is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In formula A3, R ³³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
Further, the alkyl group and aryl group in R ³¹ to R ³³ may have a substituent.
In formula A3, R ³¹ or R ³² and R ³³ may be linked to each other to form a cyclic ether, and it is preferable that R ³¹ or R ³² and R ³³ are linked to each other to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In formula A3, X ⁰ represents a single bond or an arylene group, and a single bond is preferable. The arylene group may have a substituent.
The structural unit A represented by the above formula A3 is a structural unit having a carboxy group protected by an acid-decomposable group. When the polymer A1 contains the structural unit A represented by the formula A3, the sensitivity during pattern formation is excellent, and the resolution is further excellent.

In formula A3, R ³⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the glass transition temperature (Tg) of the polymer A1 can be further lowered.
More specifically, with respect to the total amount of the structural unit A contained in the polymer A1, the structural unit in which R ³⁴ in the formula A3 is a hydrogen atom is preferably 20% by mass or more.
The content (content ratio: mass ratio) of the structural unit in which R ³⁴ in the formula A3 is a hydrogen atom in the structural unit A is calculated by a conventional method from ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of peak intensities.

Also, as preferred embodiments of the formulas A1 to A3, reference can be made to paragraphs 0044 to 0058 of International Publication No. 2018/179640.

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

The content of the structural unit A in the polymer component including the polymer A1 is preferably 10% by mass to 90% by mass, and 10% by mass to 70% by mass with respect to the total mass of the polymer component. Is more preferable, 15% by mass to 50% by mass is further preferable, and 20% by mass to 40% by mass is particularly preferable. Within the above range, the resolution is further improved.
The content (content ratio: mass ratio) of the structural unit A in the polymer component containing the polymer A1 can be confirmed by the intensity ratio of peak intensities calculated by a conventional method from ¹³ C-NMR measurement.

-Structural unit B-
The polymer A1 may include a structural unit having an acid group (also referred to as “structural unit B”).
The structural unit B is a structural unit containing a protecting group, for example, an acid group not protected by an acid-decomposable group, that is, an acid group having no protecting group. When the polymer A1 contains the structural unit B, the sensitivity during pattern formation is improved, the polymer A1 is easily dissolved in an alkaline developing solution in the developing step after pattern exposure, and the developing time can be shortened.
The acid group in the present specification means a proton dissociable group having a pKa of 12 or less. The acid group is preferably incorporated in the polymer A1 as a structural unit containing an acid group (structural unit B) using a monomer capable of forming an acid group.
From the viewpoint of improving the 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.

The polymer A1 contains the structural unit A and a structural unit B having an acid group having no protective group as a copolymerization component, and has a glass transition temperature of 90 ° C. or lower, thereby containing the polymer A1. The mold-type photosensitive resin layer has better resolution and sensitivity during pattern formation while maintaining good transferability and releasability from the temporary support.

Examples of the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group. Among them, at least one acid group selected from the group consisting of carboxy group and phenolic hydroxyl group is preferable.
Introduction of the structural unit having an acid group into the polymer A1 can be carried out by copolymerizing a monomer having an acid group.
The structural unit containing an acid group, which is the structural unit B, is derived from a structural unit derived from a styrene compound or a structural unit derived from a vinyl compound with an acid group, or derived from (meth) acrylic acid. It is more preferably a structural unit.

As the structural unit B, a structural unit having a carboxy group or a structural unit having a phenolic hydroxyl group is preferable from the viewpoint that the sensitivity during pattern formation becomes better.
The monomer having an acid group capable of forming the structural unit B is not limited to the examples described above.

The structural unit B contained in the polymer A1 may be only one type or two or more types.
The polymer A1 preferably contains the structural unit having an acid group (structural unit B) in an amount of 0.01% by mass to 20% by mass, and 0.01% by mass to 15% by mass, based on the total mass of the polymer A1. It is more preferable that the content is 0.01 to 10% by mass. Within the above range, the pattern formability becomes better.
The content (content ratio: mass ratio) of the structural unit B in the polymer A1 can be confirmed by an intensity ratio of peak intensities calculated by a conventional method from ¹³ C-NMR measurement.

-Other components-
The polymer A1 contains other structural units (hereinafter sometimes referred to as the structural unit C) other than the structural units A and B described above within a range that does not impair the effects of the transfer material according to the present disclosure. May be included.
The monomer forming the structural unit C is not particularly limited, and examples thereof include styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, and unsaturated dicarboxylic acid diester. , Bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, groups having an aliphatic cyclic skeleton, other Mention may be made of saturated compounds.
By adjusting at least one of the type and the content using the structural unit C, various properties of the polymer A1 can be adjusted. In particular, by appropriately using the structural unit C, the Tg of the polymer A1 can be easily adjusted.
By setting the glass transition temperature to 120 ° C. or less, the photosensitive resin layer containing the polymer A1 maintains the transferability and the removability from the temporary support at a good level, and the resolution and sensitivity during pattern formation. Will be better.
The polymer A1 may include only one type of the structural unit C or may include two or more types of the structural unit C.

The structural unit C is specifically styrene, methylstyrene, 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 ) A constituent unit formed by polymerizing acrylate or the like can be mentioned. In addition, compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623 can be mentioned.

From the viewpoint of resolution, the structural unit C preferably contains a structural unit having a basic group.
From the viewpoint of resolution, the basic group is preferably a group having a nitrogen atom, more preferably an aliphatic amino group, an aromatic amino group, or a nitrogen-containing heteroaromatic ring group, An aliphatic amino group or a nitrogen-containing heteroaromatic ring group is more preferable, and an aliphatic amino group is particularly preferable.
The aliphatic amino group may be any of a primary amino group, a secondary amino group, or a tertiary amino group, but from the viewpoint of resolution, a secondary amino group, or, It is preferably a tertiary amino group.
The aromatic amino group is preferably an anilino group, a monoalkylanilino group, or a dialkylanilino group, and more preferably a monoalkylanilino group or a dialkylanilino group.
The nitrogen-containing heteroaromatic ring in the nitrogen-containing heteroaromatic ring group is preferably a pyridine ring, an imidazole ring or a triazole ring, more preferably a pyridine ring or an imidazole ring, and a pyridine ring Is particularly preferable.
The nitrogen-containing heteroaromatic ring group may further have a substituent on the nitrogen-containing heteroaromatic ring. The substituent is not particularly limited, but an alkyl group is preferable, and a methyl group is more preferable.

Specific examples of the monomer forming the structural unit having a basic group include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2- (dimethylamino) ethyl methacrylate, and acrylic acid 2 , 2,6,6-Tetramethyl-4-piperidyl, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, methacrylic acid 2- (diethylamino) ethyl, 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 methacrylate, 2-morpholinoethyl acrylate, N- [3 -(Dimethylamino) propyl] acrylamide, allylamine, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole, 1-Vinyl-1,2,4-triazole and the like can be mentioned.

Further, as the structural unit C, a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton is preferable from the viewpoint of improving the electrical characteristics of the obtained transfer material. Specific examples of the monomer that forms these structural units include styrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate. , And benzyl (meth) acrylate and the like. Among them, the structural unit C is preferably a structural unit derived from cyclohexyl (meth) acrylate.

Further, as the monomer forming the structural unit C, for example, (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Above all, alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

The content of the structural unit C in the polymer component is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 50% by mass or less, based on the total mass of the polymer component. The lower limit may be 0% by mass, but is preferably 10% by mass or more, and more preferably 20% by mass or more. Within the above range, the resolution and adhesiveness are further improved.

Hereinafter, preferred examples of the polymer A1 in the present disclosure will be given, but the present disclosure is not limited to the following examples. The ratio of the constituent units and the weight average molecular weight in the following exemplified compounds are appropriately selected to obtain preferable physical properties.

-Glass transition temperature of polymer A1: Tg-
The glass transition temperature (Tg) of the polymer A1 according to the present disclosure is preferably 20 ° C. or higher, and more preferably 20 ° C. or higher and 90 ° C. or lower, from the viewpoint of further enhancing the resolution and the effect of the present disclosure. Is more preferable, 20 ° C. or more and 60 ° C. or less is more preferable, and 30 ° C. or more and 50 ° C. or less is particularly preferable.

As a method of adjusting the Tg of the polymer in the present disclosure to the preferable range described above, for example, from the Tg of the homopolymer of each constitutional unit of the target polymer and the mass ratio of each constitutional unit, a FOX formula is obtained. It is possible to control the Tg of the desired polymer using the guidelines.
Regarding the FOX formula: Tg of the homopolymer of the first constitutional unit contained in the polymer is Tg1, and the mass fraction of the copolymer of the first constitutional unit is W1, and Tg of the homopolymer of the second constitutional unit. Is Tg2 and the mass fraction of the copolymer of the second constitutional unit is W2, the Tg0 (K) of the copolymer containing the first constitutional unit and the second constitutional unit is It can be estimated according to the formula.
FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)
A copolymer having a desired Tg can be obtained by adjusting the type and mass fraction of each structural unit contained in the copolymer using the above-mentioned FOX formula.
It is also possible to adjust the Tg of the polymer by adjusting the weight average molecular weight of the polymer.

—Acid Value of Polymer A1—
From the viewpoint of resolution, the acid value of the polymer A1 is preferably 0 mgKOH / g or more and 100 mgKOH / g or less, more preferably 0 mgKOH / g or more and 50 mgKOH / g or less, and 0 mgKOH / g or more 20 mgKOH / g. It is more preferably at most g, particularly preferably at least 0 mgKOH / g and at most 10 mgKOH / g.

The acid value of the polymer in the present disclosure represents the mass of potassium hydroxide required to neutralize the acidic component per 1 g of the polymer. Specifically, the measurement sample was dissolved in a mixed solvent of tetrahydrofuran / water = 9/1 (volume ratio) and obtained using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Manufacturing Co., Ltd.). The solution is neutralized and titrated with a 0.1 mol / L sodium hydroxide aqueous solution at 25 ° C. Using the inflection point of the titration pH curve as the end point of titration, the acid value is calculated by the following formula.
A = 56.11 × Vs × 0.1 × f / w
A: Acid value (mgKOH / g)
Vs: amount of 0.1 mol / L sodium hydroxide aqueous solution used for titration (mL)
f: titer of 0.1 mol / L sodium hydroxide aqueous solution w: mass of measurement sample (g) (solid content conversion)

-Molecular weight of polymer A1: Mw-
The molecular weight of the polymer A1 is a polystyrene-equivalent weight average molecular weight, and is preferably 10,000 or more and 60,000 or less, more preferably 15,000 or more and 60,000 or less, from the viewpoint of more exerting the effect in the present disclosure. It is more preferably 20,000 or more and 50,000 or less.

The weight average molecular weight of the polymer in the present disclosure can be measured by GPC (gel permeation chromatography), and various commercially available devices can be used as the measuring device. Measurement techniques are known to those skilled in the art.
The weight average molecular weight is measured by gel permeation chromatography (GPC) using HLC (registered trademark) -8220 GPC (manufactured by Tosoh Corporation) as a measuring device and TSKgel (registered trademark) Super HZM-M (4) as a column. .6 mmID × 15 cm, manufactured by Tosoh Corporation, Super HZ4000 (4.6 mmID × 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mmID × 15 cm, manufactured by Tosoh Corporation), Super HZ2000 (4.6 mmID). It is possible to use THF (tetrahydrofuran) as an eluent by using one in which each of x15 cm, manufactured by Tosoh Corp.) is connected in series.
The measurement conditions are as follows: a sample concentration of 0.2 mass%, a flow rate of 0.35 ml / min, a sample injection amount of 10 μL, and a measurement temperature of 40 ° C., using a differential refractive index (RI) detector. be able to.
The calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A-5000”, It can be manufactured using any of the seven samples of "A-2500" and "A-1000".

The ratio (dispersion) of the number average molecular weight and the weight average molecular weight of the polymer A1 is preferably 1.0 to 5.0, and more preferably 1.05 to 3.5.

-Method for producing polymer A1-
The production method (synthesis method) of the polymer A1 is not particularly limited, but an example thereof is a monomer for forming the structural unit A, and optionally a polymerizable monomer for forming the other structural unit C. It can be synthesized by polymerizing using a polymerization initiator in an organic solvent containing a monomer. It can also be synthesized by a so-called polymer reaction.

The content of the polymer component in the positive photosensitive resin layer in the present disclosure is 75% by mass with respect to the total mass of the photosensitive resin layer, from the viewpoint of suppressing the generation of streaks and the adhesion on the transfer surface during transfer. % Or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 90% by mass to 99.9% by mass.
The content of the polymer A1 in the positive photosensitive resin layer is 75% by mass to 99.9% by mass based on the total mass of the positive photosensitive resin layer from the viewpoint of suppressing wiring defects and resolution. %, More preferably 80% by mass to 99% by mass, and particularly preferably 90% by mass to 95% by mass.

[Other polymers]
The positive photosensitive resin layer does not include, as a polymer component, a structural unit having an acid group protected by an acid-decomposable group, in addition to the polymer A1, as long as the effect of the transfer material according to the present disclosure is not impaired. It may further contain a polymer (sometimes referred to as "other polymer").
Unless otherwise specified, the polymer component in the present disclosure is meant to include, in addition to the polymer A1, other polymers optionally added. The compounds corresponding to the cross-linking agent, the dispersant, and the surfactant, which will be described later, are not included in the polymer component even if they are polymer compounds.
When the positive photosensitive resin layer contains another polymer, the content of the other polymer is preferably 50% by mass or less, and more preferably 30% by mass or less, based on all the polymer components. Is more preferably 20% by mass or less.

The positive photosensitive resin layer may contain only one type of other polymer in addition to the polymer A1, or may contain two or more types thereof.
As another polymer, for example, polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer). , ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (all produced by Toagosei Co., Ltd.), and Joncryl 690, Joncr. , Joncryl 67, and Joncryl 586 (all manufactured by BASF) can also be used.

[Photo acid generator]
The positive photosensitive resin layer preferably contains a photoacid generator.
The photo-acid generator used in the present disclosure is a compound capable of generating an acid when irradiated with an actinic ray such as an ultraviolet ray, a far ultraviolet ray, an X-ray or an electron beam.
The photo-acid generator used in the present disclosure is preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm to generate an acid, but its chemical structure is not limited. Further, regarding a photo-acid generator which is not directly sensitive to an actinic ray having a wavelength of 300 nm or more, when it is used in combination with a sensitizer, it is a compound which is sensitive to an actinic ray having a wavelength of 300 nm or more and generates an acid. It can be preferably used in combination.
The photoacid generator used in the present disclosure 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 a pKa of 2 or less. Particularly preferred are photoacid generators that generate the above acid. The lower limit of pKa is not particularly limited, but is preferably -10.0 or more, for example.

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 such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Of these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.
As the ionic photoacid generator, the ionic photoacid generator described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.
Examples of nonionic photoacid generators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, the photoacid generator is preferably an oxime sulfonate compound from the viewpoint of sensitivity, resolution, and adhesion. Specific examples of trichloromethyl-s-triazines, diazomethane compounds, and imidosulfonate compounds include the compounds described in paragraphs 0083 to 0088 of JP 2011-221494A.

As the oxime sulfonate compound, those described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 can be preferably used.

From the viewpoint 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, and more preferably contains oxime sulfonate compounds. ..
In addition, examples of preferable photoacid generators include photoacid generators having the following structures.

The positive photosensitive resin layer may contain one type of photoacid generator alone, or may contain two or more types.
From the viewpoint of sensitivity and resolution, the content of the photo-acid generator in the positive photosensitive resin layer is preferably 0.1% by mass to 10% by mass based on the total mass of the positive photosensitive resin layer. More preferably 0.5% by mass to 5% by mass.

[Other additives]
The positive photosensitive resin layer in the present disclosure may contain other additives, if necessary, in addition to the polymer component containing the polymer A1, the photoacid generator and the solvent.
As other additives, known ones can be used, and examples thereof include a plasticizer, a sensitizer, a heterocyclic compound, an alkoxysilane compound, a basic compound, a rust preventive, and a surfactant.
Examples of the plasticizer, sensitizer, heterocyclic compound and alkoxysilane compound include those described in paragraphs 0097 to 0119 of WO2018 / 179640.

-Basic compound-
The positive photosensitive resin layer preferably further contains a basic compound.
As the basic compound, any of the basic compounds used in the chemically amplified resist can be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include the compounds described in paragraphs 0204 to 0207 of JP 2011-221494A, the contents of which are incorporated herein.

Specifically, examples of the aliphatic amine include di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, dicyclohexylamine, dicyclohexylmethylamine and the like. Be done.
Examples of aromatic amines include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
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, nicotinic acid amide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7 -For example, Undecen.
As the basic compound, N-cyclohexyl-N '-[2- (4-morpholinyl) ethyl] thiourea (CMTU) can be preferably used. Commercial products of CMTU include those manufactured by Toyo Kasei Co., Ltd.

As the basic compound, a benzotriazole compound is preferable from the viewpoint of the linearity of the conductive wiring when applied to the formation of a conductive pattern.

The benzotriazole compound is not limited as long as it has a benzotriazole skeleton, and a known benzotriazole compound can be used.
Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 5-carboxybenzotriazole, 1- (hydroxymethyl) -1H -Benzotriazole, 1-acetyl-1H-benzotriazole, 1-aminobenzotriazole, 9- (1H-benzotriazol-1-ylmethyl) -9H-carbazole, 1-chloro-1H-benzotriazole, 1- (2- Pyridinyl) benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-ethylbenzotriazole, 1- (1'-hydroxyethyl) benzotriazole, 1- (2'-hydroxyethyl) benzotriazole, 1-propyl Benzotriazole, 1- (1'-hydroxypropyl) benzotriazole, 1- (2'-hydroxypropyl) benzotriazole, 1- (3'-hydroxypropyl) benzotriazole, 4-hydroxy-1H-benzotriazole, 5- Methyl-1H-benzotriazole, methylbenzotriazole-5-carboxylate, ethylbenzotriazole-5-carboxylate, t-butyl-benzotriazole-5-carboxylate, cyclopentylethyl-benzotriazole-5-carboxylate, 1H- Examples thereof include benzotriazole-4-sulfonic acid, 1H-benzotriazole-1-acetonitrile, 1H-benzotriazole-1-carboxaldehyde, 2-methyl-2H-benzotriazole and 2-ethyl-2H-benzotriazole.

The positive photosensitive resin layer may contain one type of basic compound or two or more types of basic compounds.
The content of the basic compound is preferably 0.001% by mass to 5% by mass, and more preferably 0.005% by mass to 3% by mass, based on the total mass of the positive photosensitive resin layer. preferable.

-Surfactant-
The positive photosensitive resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
As the surfactant, any of anionic, cationic, nonionic (nonionic) or amphoteric surfactants can be used, but the preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. .. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by JEMCO), Megafac (manufactured by DIC Co., Ltd.), and Florard (Sumitomo 3M Co., Ltd.) Asahi Glass, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (manufactured by Toray Dow Corning Co., Ltd.).

As the surfactant, for example, the surfactants described in paragraphs 0120 to 0125 of International Publication No. 2018/179640 can be used.
As a commercially available product of the surfactant, for example, Megafac F-552 or F-554 (above, manufactured by DIC Corporation) can be used.
In addition, the surfactants described in Paragraph 0017 of Japanese Patent No. 4502784 and Paragraph 0060 to Paragraph 0071 of Japanese Patent Laid-Open No. 2009-237362 can be used.

The positive photosensitive resin layer may contain one type of surfactant alone, or may contain two or more types of surfactant.
The content of the surfactant is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and 0.01% by mass or less with respect to the total mass of the positive photosensitive resin layer. More preferably, it is from 3% by mass to 3% by mass.

Further, in the positive photosensitive resin layer in the present disclosure, as other additives, metal oxide particles, antioxidants, dispersants, acid proliferating agents, development accelerators, conductive fibers, colorants, thermal radical polymerization. Known additives such as an initiator, a thermal acid generator, an ultraviolet absorber, a thickener, a cross-linking agent, and an organic or inorganic suspending agent can be further added.
Preferred embodiments of these components are described in paragraphs 0165 to 0184 of JP-A-2014-85643, and the contents of this publication are incorporated herein.

Further, the positive photosensitive resin layer in the transfer material according to the present disclosure may contain a solvent. When the positive photosensitive resin layer is formed from the photosensitive resin composition containing a solvent, the solvent may remain.
The content of the solvent in the positive photosensitive resin layer is preferably 5% by mass or less, more preferably 2% by mass or less, and 1% by mass or less with respect to the total mass of the photosensitive resin layer. More preferably.

<< Average Thickness of Positive Photosensitive Resin Layer >>
The average thickness of the positive photosensitive resin layer is preferably 0.5 μm to 20 μm. When the average thickness of the positive photosensitive resin layer is 20 μm or less, the pattern resolution is more excellent, and when it is 0.5 μm or more, it is preferable from the viewpoint of pattern linearity.
The average thickness of the positive photosensitive resin layer is more preferably 0.8 μm to 15 μm, particularly preferably 1.0 μm to 10 μm.

<< Method of forming positive photosensitive resin layer >>
The positive photosensitive resin layer in the present disclosure may be formed by adjusting, coating and drying a photosensitive resin composition containing components necessary for forming the positive photosensitive resin layer and a solvent. it can. Specifically, each component and a solvent are mixed at an arbitrary ratio and in an arbitrary method, and dissolved by stirring to prepare a photosensitive resin composition for forming a positive photosensitive resin layer. . For example, it is possible to prepare a composition by dissolving each component in advance in a solvent and then mixing the obtained solutions at a predetermined ratio. The composition prepared as described above may be filtered using, for example, a filter having a pore size of 0.2 μm to 30 μm.

The positive photosensitive resin layer in the present disclosure can be formed by applying the photosensitive resin composition on a temporary support or a cover film and drying it.
The coating method is not particularly limited, and it can be coated by a known method such as slit coating, spin coating, curtain coating, inkjet coating and the like.
Further, the photosensitive resin layer can be formed on the temporary support or the cover film on which other layers described below are formed.

[Photosensitive resin composition]
The photosensitive resin composition preferably contains a component contained in the positive photosensitive resin layer and a solvent. A photosensitive resin layer can be preferably formed by incorporating a solvent into each component to adjust the viscosity, and applying and drying.

-solvent-
Examples of the solvent include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl-n-butyl ether, propylene glycol methyl-n-propyl ether, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether. Propionate, dipropylene glycol methyl ether acetate, 3-methoxybutyl ether acetate, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol diacetate, diethylene glycol monoethyl ether acetate, dipropylene glycol dimethyl ether, and 1,3-butylene glycol diester Known solvents such as acetate and the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 can be mentioned.

Further, the solvent preferably contains a solvent having a vapor pressure at 20 ° C. of 1 kPa or more and 16 kPa or less, or a mixture thereof. Solvents having a vapor pressure at 20 ° C. of 1 kPa or more and 16 kPa or less include ethyl acetate, propyl acetate, isopropyl acetate, isobutyl acetate, butyl acetate, tert-butyl acetate, cyclopentyl methyl ether, diisopropyl ether, propylene glycol monoethyl ether, methyl n. -Butyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, toluene, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, 1,2-propanediol diacetate, Preferable examples include 1,3-butanediol diacetate, 1,6-hexanediol diacetate, triacetin, dipropylene glycol-n-butyl ether, and diethylene glycol monobutyl ether acetate.
The solvent that can be used in the present disclosure may be used alone or in combination of two.

The content of the solvent at the time of applying the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. It is more preferably from about 900 parts by mass.

<Temporary support>
The transfer material according to the present disclosure has a temporary support.
The temporary support is a support that supports the intermediate layer and the photosensitive resin layer and can be peeled off.
The temporary support used in the present disclosure may have light transmittance from the viewpoint of exposing the intermediate layer and the photosensitive resin layer through the temporary support when the intermediate layer and the photosensitive resin layer are subjected to pattern exposure. preferable.
Having light transmittance means that the transmittance of the main wavelength of the light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of the light used for pattern exposure is from the viewpoint of improving the exposure sensitivity. Therefore, 60% or more is preferable, and 70% or more is more preferable. As a method of measuring the transmittance, there is a method of measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
Examples of the temporary support include a glass substrate, a resin film, paper and the like, and a resin film is particularly preferable from the viewpoint of strength and flexibility. Examples of the resin film include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, polycarbonate film and the like. Of these, a biaxially stretched polyethylene terephthalate film is particularly preferable.

The average thickness of the temporary support is not particularly limited, but is preferably in the range of 5 μm to 200 μm, more preferably in the range of 10 μm to 150 μm from the viewpoint of ease of handling and versatility.
The thickness of the temporary support depends on the material, from the viewpoint of strength as a support, flexibility required for bonding with a circuit wiring forming substrate, and light transmission required in the first exposure step. Just select it.

Preferred embodiments of the temporary support are described, for example, in paragraphs 0017 to 0018 of JP-A-2014-85643, the contents of which are incorporated into the present disclosure.

<Cover film>
The transfer material according to the present disclosure preferably has a cover film on the surface of the transfer material opposite to the surface on which the temporary support is provided.
Examples of the cover film include a resin film and paper, and a resin film is particularly preferable from the viewpoint of strength and flexibility. Examples of the resin film include polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film and polycarbonate film. Among them, polyethylene film, polypropylene film and polyethylene terephthalate film are preferable.

The average thickness of the cover film is not particularly limited, and for example, one having a thickness of 1 μm to 2 mm is preferable.

<Other layers>
The transfer material according to the present disclosure may have a layer other than those described above (hereinafter, also referred to as “other layer”). Examples of other layers include a contrast enhancement layer and a thermoplastic resin layer.
A preferred embodiment of the contrast enhancement layer is paragraph 0134 of International Publication No. 2018/179640, a preferred embodiment of the thermoplastic resin layer is paragraph 0189 to paragraph 0193 of JP-A-2014-85643, and further preferred are other layers. Aspects are described in paragraphs 0194 to 0196 of JP-A-2014-85643, and the contents of this publication are incorporated herein.

Here, referring to FIG. 1, an example of a layer configuration of a transfer material according to the present disclosure is schematically illustrated.
In the transfer material 100 shown in FIG. 1, a temporary support 10, an intermediate layer 12, a photosensitive resin layer 14, and a cover film 16 are laminated in this order.

(Resin pattern manufacturing method and circuit wiring manufacturing method)
The method for producing a resin pattern according to the present disclosure is not particularly limited as long as it is a method for producing a resin pattern using the transfer material according to the present disclosure. However, it is photosensitive to the temporary support in the transfer material according to the present disclosure. Of the outermost layer on the side having the photosensitive resin layer to the substrate for bonding (hereinafter, sometimes referred to as “bonding step”) and pattern exposing the photosensitive resin layer (hereinafter, “exposure step”). ") And a step of developing the exposed photosensitive resin layer to form a pattern (hereinafter sometimes referred to as" developing step ").
Further, the substrate in the method for producing a resin pattern according to the present disclosure is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on its surface.
Further, the method for producing a circuit wiring according to the present disclosure is not particularly limited as long as it is a method for producing a circuit wiring using the transfer material according to the present disclosure, but is not limited to the temporary support in the transfer material according to the present disclosure. A step of bringing the outermost layer on the side having the photosensitive resin layer into contact with the substrate having the conductive layer and adhering the same, a step of pattern-exposing the photosensitive resin layer, and a step of developing the exposed photosensitive resin layer. It is preferable to include a step of forming a pattern and a step of etching the conductive layer in a region where the pattern is not arranged (hereinafter, sometimes referred to as “etching step”) in this order.
Further, the substrate in the method for manufacturing circuit wiring according to the present disclosure is preferably a substrate having the conductive layer on its surface.
In addition, a method for manufacturing a resin pattern according to the present disclosure, and a method for manufacturing a circuit wiring according to the present disclosure include a method of forming the temporary support after the step of bonding to the substrate and before the step of forming the pattern. It is preferable to include a step of peeling.

The above-mentioned photosensitive resin layer is of a positive type, which leaves as an image the portion not irradiated with actinic rays. In the positive type photosensitive resin layer, by irradiating with actinic rays, for example, the solubility of the exposed areas is increased by using, for example, a photosensitizer which generates acid upon irradiation with the active rays. If none of the exposed parts are cured and the obtained pattern shape is defective, the substrate can be reused (reworked) by exposing the entire surface. Further, since the technique of exposing the remaining photosensitive resin layer again to form a different pattern can be realized only by the positive type photosensitive resin layer, the method of manufacturing a resin pattern according to the present disclosure, or the present disclosure. In the method of manufacturing the circuit wiring, a mode in which the exposure is performed twice or more is preferably mentioned.

Examples of the mode in which the exposure is performed twice or more include the modes described below.
The circuit wiring manufacturing method according to the present disclosure preferably includes a mode in which four steps of the bonding step, the exposure step, the developing step, and the etching step are set as one set and repeated a plurality of times.
In the method for manufacturing a circuit wiring according to the present disclosure, after performing the bonding step, the exposure step, the developing step, and the etching step, the exposure step is further performed on the pattern. A preferred mode is one in which the developing step and the etching step are subsequently performed.

<Laminating process>
A method for producing a resin pattern according to the present disclosure, or a method for producing a circuit wiring according to the present disclosure, wherein the outermost layer having a photosensitive resin layer with respect to the temporary support in the transfer material according to the present disclosure is a substrate It is preferable to include a step (bonding step) of bringing the substrate having a conductive layer into contact therewith.
Further, in the bonding step, it is preferable that the conductive layer and the outermost layer on the side having the photosensitive resin layer with respect to the temporary support in the transfer material according to the present disclosure are pressure-bonded to each other. . In the above aspect, the patterned photosensitive resin layer after exposure and development can be suitably used as an etching resist when etching the conductive layer.
The method for press-bonding the substrate and the transfer material is not particularly limited, and known transfer methods and laminating methods can be used.
Specifically, for example, the outermost layer side having the photosensitive resin layer with respect to the temporary support in the transfer material is overlaid on a substrate, and pressure is applied by a roll, or pressure and heat are applied. It is preferably carried out. For laminating, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of improving productivity can be used.
The pressure and temperature of the bonding step in the bonding step are not particularly limited, depending on the material of the surface of the substrate to be bonded, for example, the material of the conductive layer, the material of the outermost layer, the transport speed, and the pressure bonding machine to be used. It can be set appropriately. When the transfer material has a cover film, the cover film may be removed and then pressure-bonded.
When the base material is a resin film, roll-to-roll pressure bonding may be performed.

The substrate used in the present disclosure is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface of a base material. Wiring is formed by patterning the conductive layer. Further, in the present disclosure, a film base material such as polyethylene terephthalate is preferably provided with a plurality of conductive layers such as metal oxides and metals.
In addition, the substrate used in the present disclosure is preferably a substrate containing copper from the viewpoint of exerting the effect in the present disclosure more. Further, from the viewpoint of more exerting the effect in the present disclosure, the conductive layer is preferably a layer containing copper.

Further, the substrate is preferably a substrate in which a plurality of conductive layers are laminated on a support.
In the substrate in which a plurality of conductive layers are laminated on the support, the support is preferably a glass base material or a film base material, and more preferably a film base material. In the method of manufacturing circuit wiring according to the present disclosure, in the case of touch panel circuit wiring, it is particularly preferable that the support is a sheet-shaped resin composition.
Further, the support is preferably transparent.
The refractive index of the support is preferably 1.50 to 1.52.
The support may be composed of a translucent base material such as a glass base material, and a tempered glass typified by Gorilla glass manufactured by Corning Incorporated can be used. Further, as the above-mentioned transparent substrate, the materials used in JP 2010-86684 A, JP 2010-152809 A and JP 2010-257492 A can be preferably used.
When a film base material is used as the base material, it is more preferable to use a base material having no optical distortion and a base material having high transparency, and specific materials include polyethylene terephthalate (PET), Examples thereof include polyethylene naphthalate, polycarbonate, triacetyl cellulose and cycloolefin polymer.

The conductive layer may be any conductive layer used for general wiring or touch panel wiring.
Examples of the material of the conductive layer include metals and metal oxides.
Examples of the metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ₂ . Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr and Mo.

In the method of manufacturing a resin pattern according to the present disclosure or the method of manufacturing a circuit wiring according to the present disclosure, it is preferable that at least one conductive layer of the plurality of conductive layers contains a metal oxide.
The conductive layer is preferably an electrode pattern corresponding to the sensor of the visual recognition part used in the capacitive touch panel or a wiring of the peripheral extraction part.

<Exposure process>
The method for producing a resin pattern according to the present disclosure or the method for producing a circuit wiring according to the present disclosure preferably includes a step (exposure step) of pattern-exposing the photosensitive resin layer after the attaching step.
In the exposure step, it is preferable that the photosensitive resin layer is irradiated with an actinic ray through a mask having a predetermined pattern. In this step, the photo-acid generator decomposes to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the photosensitive resin layer is hydrolyzed to generate an acid group such as a carboxy group or a phenolic hydroxyl group.
In the present disclosure, the detailed arrangement and specific size of the pattern are not particularly limited. In order to improve the display quality of a display device (for example, a touch panel) provided with an input device having a circuit board manufactured according to the present disclosure, and to make the area occupied by the extraction wiring as small as possible, at least a part of the pattern (particularly the touch panel). The electrode pattern and the lead-out wiring) are preferably 100 μm or less, and more preferably 70 μm or less.
Further, the exposure in the exposure step may be exposure through a mask or digital exposure using a laser or the like, but exposure through a mask for exposure is preferable.
The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure includes a step of bringing the transfer material into contact with an exposure mask between the bonding step and the exposure step. It is preferable. In the above aspect, the resolution of the obtained pattern is more excellent.

Examples of the actinic rays include visible rays, ultraviolet rays, and electron rays. Visible rays or ultraviolet rays are preferable, and ultraviolet rays are particularly preferable.
As an exposure light source for actinic rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a light-emitting diode (LED) light source, an excimer laser generator, etc. can be used, and g-line (436 nm), i-line (365 nm) , Actinic rays having a wavelength of 300 nm or more and 450 nm or less such as h-line (405 nm) can be preferably used. Irradiation light can be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, and a bandpass filter, if necessary.
As the exposure device, various types of exposure devices such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
Exposure dose, depending on the photosensitive resin layer to be used may be appropriately ^selected, but is preferably from 5mJ / cm 2 ~ 200mJ / cm 2, more preferably 10mJ / cm 2 ~ 100mJ / cm 2 .
Further, it is also preferable to perform heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure. By a process called so-called PEB (Post Exposure Bake), it is possible to reduce the roughness of the pattern edge due to the standing wave generated in the photosensitive resin layer at the time of exposure.

Even if the pattern exposure is performed after peeling the temporary support from the photosensitive resin layer, before the peeling of the temporary support, the pattern support is exposed through the temporary support, and then the temporary support is peeled off. Good. The pattern exposure may be exposure through a mask or digital exposure using a laser or the like.

<Developing process>
In the method for producing a resin pattern according to the present disclosure or the method for producing a circuit wiring according to the present disclosure, after the exposing step, a step of developing the exposed photosensitive resin layer to form a pattern (developing step) It is preferable to include
When the transfer material has an intermediate layer, in the developing step, the exposed intermediate layer is also removed together with the exposed photosensitive resin layer. Further, in the developing step, the intermediate layer in the unexposed area may be removed in a form of being dissolved or dispersed in the developing solution.
Development of the exposed photosensitive resin layer in the developing step can be performed using a developer.
The developer is not particularly limited as long as it can remove the exposed portion of the photosensitive resin layer, and a known developer such as the developer described in JP-A-5-72724 can be used. . The developing solution is preferably a developing solution in which the exposed portion of the photosensitive resin layer has a dissolution type developing behavior. As the developing solution, an alkaline aqueous solution is preferable, and for example, an alkaline aqueous solution containing a compound having pKa of 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is more preferable. The developer may further contain an organic solvent miscible with water, a surfactant and the like. Examples of the developer preferably used in the present disclosure include the developers described in paragraph 0194 of WO 2015/093271.

The developing system is not particularly limited, and may be paddle development, shower development, shower and spin development, dip development or the like. Explaining shower development here, the exposed portion can be removed by spraying a developing solution onto the photosensitive resin layer after exposure with a shower. Further, after development, it is preferable to remove a development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The liquid temperature of the developer is preferably 20 ° C to 40 ° C.
Further, the longer the time from exposure to development is, the more the effect of suppressing the deformation of the pattern shape in the present disclosure is exhibited. Development may be carried out immediately after exposure, but the time from exposure to development is preferably 0.5 hours or more, more preferably 1 hour or more, still more preferably 6 hours or more, after which the development is carried out. The effect of suppressing the deformation of the pattern shape according to the present disclosure is more exerted.
In addition, the method of manufacturing a resin pattern according to the present disclosure, or the method of manufacturing a circuit wiring according to the present disclosure, such as a step of washing with water or the like after development, a step of drying the substrate having the obtained pattern, etc. May be included.

Further, it may have a post-baking step of heating the pattern obtained by development.
The post-baking heating is preferably performed in an environment of 8.1 kPa to 121.6 kPa, more preferably 50.66 kPa or more. On the other hand, it is more preferably performed in an environment of 111.46 kPa or less, and particularly preferably in an environment of 101.3 kPa or less.
The post-baking temperature is preferably 80 ° C. to 250 ° C., more preferably 110 ° C. to 170 ° C., and particularly preferably 130 ° C. to 150 ° C.
The post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
Post bake may be performed in an air environment or a nitrogen substitution environment.

The transport speed of the support at each step in the method of manufacturing a resin pattern according to the present disclosure or the method of manufacturing a circuit wiring according to the present disclosure is not particularly limited, but 0.5 m / It is preferably from min to 10 m / min, and more preferably from 2.0 m / min to 8.0 m / min except during exposure.

<Temporary support peeling process>
A method of manufacturing a resin pattern according to the present disclosure, or a method of manufacturing a circuit wiring according to the present disclosure, peels the temporary support after a step of bonding to the substrate and before a step of forming the pattern. It is preferable to include a step (temporary support peeling step).
The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure uses the above transfer material, and therefore the temporary support is peeled off after the transfer material is bonded and at any timing before development. However, since the adhesiveness to the photosensitive resin layer is excellent, it is possible to suppress the occurrence of defective factors such as partial peeling, and it is possible to perform good pattern formation.
Further, the method for producing a resin pattern according to the present disclosure, or the method for producing a circuit wiring according to the present disclosure, from the viewpoint of pattern formability and resolution, after the step of bonding to the substrate, and the photosensitive resin layer It is more preferable to include a step of peeling the temporary support before the step of pattern exposure. Further, in the above aspect, when the mask is brought into contact with the substrate for pattern exposure, the photosensitive resin layer and the mask do not come into direct contact with each other, and therefore the pattern formability and the resolution are superior.
The method of peeling the temporary support in the peeling step is not particularly limited and may be a known method.

<Cover film peeling process>
When the transfer material according to the present disclosure has a cover film, the method of manufacturing a resin pattern according to the present disclosure or the method of manufacturing a circuit wiring according to the present disclosure includes a step of peeling the cover film of the transfer material (“cover film”). It may be referred to as a "peeling step"). The method of peeling off the cover film is not limited, and a known method can be applied.

<Etching process>
The circuit wiring manufacturing method according to the present disclosure preferably includes a step (etching step) of etching the conductive layer in a region where the pattern is not arranged.
In the etching step, the pattern formed from the photosensitive resin layer in the developing step is used as an etching resist, and the conductive layer is etched.
As the etching of the conductive layer, etching can be applied by a known method such as the method described in paragraphs 0048 to 0054 of JP 2010-152155 A, a method by dry etching such as a known plasma etching, or the like.
For example, as an etching method, a generally used wet etching method of immersing in an etching solution can be mentioned. As the etching solution used for wet etching, an acidic type or alkaline type etching solution may be appropriately selected according to the object of etching.
The acidic type etching solution includes hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, or an aqueous solution containing only an acidic component such as phosphoric acid, an acidic component and ferric chloride, ammonium fluoride, or permanganese. Examples include mixed aqueous solutions of salts such as potassium acid. As the acidic component, a component obtained by combining a plurality of acidic components may be used.
As the alkaline type etching solution, an aqueous solution containing only an alkali component such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine, or a salt of an organic amine such as tetramethylammonium hydroxide, an alkali component and potassium permanganate. Examples include mixed aqueous solutions of salts such as. As the alkaline component, a component obtained by combining a plurality of alkaline components may be used.

The temperature of the etching solution is not particularly limited, but it is preferably 45 ° C or lower. In the present disclosure, the pattern used as the etching mask (etching pattern) preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in the temperature range of 45 ° C. or lower. Therefore, the pattern is prevented from peeling during the etching process, and the portion where the pattern does not exist is selectively etched.

After the etching step, in order to prevent contamination of the process line, a step of cleaning the etched substrate (washing step) and a step of drying the etched substrate (drying step) are performed as necessary. Good. Examples of the cleaning step include cleaning the substrate with pure water at room temperature (10 ° C. to 35 ° C.) for 10 seconds to 300 seconds. In the drying step, for example, air blow may be used, and the air blow pressure (about 0.1 kg / cm ² to 5 kg / cm ² ) may be appropriately adjusted to perform the drying.

<Etching resist stripping process>
It is preferable that the circuit wiring manufacturing method according to the present disclosure includes a step of removing the photosensitive resin layer with a release solution (etching resist removing step) after the etching step.
After the completion of the etching step, the patterned photosensitive resin layer remains. If the photosensitive resin layer is unnecessary, all the remaining photosensitive resin layer may be removed.
As a method of peeling using a peeling solution, for example, a substrate having the above-mentioned photosensitive resin layer or the like in the peeling solution is stirred for 5 minutes at preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. Examples include a method of soaking for about 30 minutes.
As the stripping solution, for example, an inorganic alkali component such as sodium hydroxide or potassium hydroxide, or an organic alkali component such as a tertiary amine or a quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or A stripping solution dissolved in these mixed solutions can be used. A stripping solution may be used and stripping may be performed by a spray method, a shower method, a paddle method, or the like.

Further, in the circuit wiring manufacturing method according to the present disclosure, the exposure step, the development step, and the etching step may be repeated twice or more as necessary.
As examples of the exposure step, the development step, and other steps in the present disclosure, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be preferably used in the present disclosure.

-Overall exposure of positive photosensitive resin layer-
When the photosensitive resin layer in the transfer material according to the present disclosure is a positive type photosensitive resin layer, the method for manufacturing a circuit wiring according to the present disclosure includes a step of exposing the entire surface of the positive type photosensitive resin layer after the etching step. (Hereinafter, it may be referred to as "entire surface exposure step".) And a step of removing the positively exposed photosensitive resin layer that has been entirely exposed.
In the conventional circuit wiring manufacturing method, when the etching mask removing solution is used for a long time, the etching mask removing property may gradually decrease. After the etching process, by exposing the positive photosensitive resin layer used as the etching mask to the entire surface, the solubility in the removal liquid and the permeability of the removal liquid are improved, and the removal liquid is removed even when used for a long time. Excellent in performance.
Further, a circuit wiring is manufactured by repeatedly applying the circuit wiring manufacturing method to a substrate having a base material and a plurality of conductive layers including a first conductive layer and a second conductive layer that are different in constituent materials from each other. You can also
The step of removing the positive-type photosensitive resin layer exposed on the entire surface can be performed by the same method as the above-mentioned etching resist removing step.

<Overall exposure process>
In the whole surface exposure step, all of the positive photosensitive resin layer that causes an afterimage due to development may be exposed, and the portion without the positive photosensitive resin layer may or may not be exposed. From the viewpoint of simplicity, it is preferable to expose the entire surface of the substrate on the side having the positive photosensitive resin layer, for example.

The light source used for the exposure in the whole surface exposure process is not particularly limited, and a known exposure light source can be used. From the viewpoint of removability, it is preferable to use a light source containing light having the same wavelength as that in the exposure step.

The exposure amount in the overall exposure step, from the viewpoint of removability is ^preferably 5mJ / cm 2 ~ 1,000mJ / cm 2, more preferably 10mJ / cm 2 ~ 800mJ / cm 2, 100mJ / Particularly preferably, it is cm ² to 500 mJ / cm ² .

From the viewpoint of removability, the exposure amount in the whole surface exposure process is preferably equal to or more than the exposure amount in the above exposure process, and more preferably more than the exposure amount in the above exposure process.

<Heating process>
A method for manufacturing a circuit wiring according to the present disclosure includes a step of heating the above-described whole-surface-exposed positive photosensitive resin layer during the whole-surface exposure step, after the exposure step, or both, and before a removing step described later. (Hereinafter, it may be called a "heating process.") By including the heating step, the reaction rate of the photo-acid generator and the reaction rate of the generated acid and the positive photosensitive resin can be further improved, and as a result, the removal performance is improved.

The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure may include other arbitrary steps. For example, the following steps may be mentioned, but the present invention is not limited to these steps.

<Process of reducing visible light reflectance>
The circuit wiring manufacturing method according to the present disclosure can include a step of reducing the visible light reflectance of the surface of the conductive layer, for example, part or all of the surface of the conductive layer on the substrate. ..
Examples of the treatment for lowering the visible light reflectance include oxidation treatment. For example, the visible light reflectance can be reduced by blackening by oxidizing copper to copper oxide.
For preferred embodiments of the treatment for reducing the visible light reflectance, see paragraphs 0017 to 0025 of JP-A-2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of JP-A-2013-206315. There is a description and the content of this publication is incorporated herein.

<Step of forming an insulating film on the etched substrate, and step of forming a new conductive layer on the insulating film>
A method of manufacturing circuit wiring according to the present disclosure includes a step of forming an insulating film on the substrate, for example, the formed wiring (etched conductive layer), and a step of forming a new conductive layer on the insulating film. It is also preferable to include.
The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be used. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
There is no particular limitation on the step of forming a new conductive layer on the insulating film. A new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

In the method for manufacturing a circuit wiring according to the present disclosure, the new conductive layer may be etched by forming an etching resist by the same method as described above, or may be separately etched by a known method. .
The substrate having circuit wiring obtained by the method for manufacturing circuit wiring according to the present disclosure may have wiring of only one layer or wiring of two or more layers on the substrate.

Further, in the method for manufacturing a circuit wiring according to the present disclosure, the substrate may have a plurality of conductive layers on both surfaces, and circuits may be sequentially or simultaneously formed on the conductive layers formed on both surfaces of the substrate. preferable. With such a configuration, a wiring in which a first conductive pattern (first wiring) is formed on one surface of the substrate and a second conductive pattern (second wiring) is formed on the other surface, preferably a touch panel wiring Can be formed.

~ Roll to roll method ~
The resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure is preferably performed by a roll-to-roll method.
The roll-to-roll method uses a substrate that can be wound and unwound as a substrate, and unwinds the substrate or a structure including the substrate before any step included in the method for manufacturing circuit wiring ( Hereinafter, it may be referred to as a "winding step"), and a step of winding a structure including a base material or a substrate after any one of the steps (hereinafter, may be referred to as a "winding step"). , And at least one of the steps (preferably all steps or all steps other than the heating step) is carried out while the structure including the base material or the substrate is carried.
The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and known methods may be used in the manufacturing method to which the roll-to-roll method is applied.

The circuit wiring according to the present disclosure is a circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present disclosure.
A substrate having circuit wiring according to the present disclosure is a substrate having circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure.
The application of the substrate having the circuit wiring according to the present disclosure is not limited, but it is preferably a circuit wiring board for a touch panel, for example.

An input device is an example of a device including circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure.
The input device according to the present disclosure may be any input device that has at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure, and is preferably a touch panel, and more preferably a capacitive touch panel. preferable.
The display device according to the present disclosure preferably includes the input device according to the present disclosure. The display device according to the present disclosure is preferably an image display device such as an organic EL display device and a liquid crystal display device.

(Method for manufacturing touch panel)
The method for manufacturing a touch panel according to the present disclosure is not particularly limited as long as it is a method for manufacturing a touch panel using the transfer material according to the present disclosure, but a positive photosensitive resin of the transfer material with respect to the temporary support is used. A step of laminating the outermost layer on the side having a layer to a substrate having a conductive layer (hereinafter, also referred to as "laminating step"), and the positive photosensitive resin of the transfer material after the laminating step A step of pattern-exposing the layer (hereinafter sometimes referred to as "exposure step"), and a step of developing the positive photosensitive resin layer after the step of pattern-exposing to form a resin pattern (hereinafter, "development" It may be referred to as “process”) and a process of etching the substrate in the region where the resin pattern is not arranged (hereinafter, may be referred to as “etching process”) in this order.
The touch panel manufacturing method according to the present disclosure preferably includes a step of peeling the temporary support (temporary support peeling step) after the bonding step and before the developing step.
The touch panel manufacturing method according to the present disclosure may include a step of peeling the cover film of the transfer material (cover film peeling step) before the bonding step.

In the method for manufacturing a touch panel according to the present disclosure, the temporary support peeling step, the laminating step, the exposing step, the developing step, the etching step, and the cover film peeling step, specific aspects of each step, the above-mentioned "circuit wiring As described in the section of “Production method”, the preferred embodiment is also the same.

A touch panel according to the present disclosure is a touch panel including at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure. In addition, the touch panel according to the present disclosure preferably has at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
The detection method in the touch panel according to the present disclosure may be any known method such as a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Of these, the capacitance method is preferable.
As the touch panel type, a so-called in-cell type (for example, those described in FIGS. 5, 6, 7, and 8 of Japanese Patent Publication No. 2012-517051), a so-called on-cell type (for example, Japanese Unexamined Patent Publication No. 2013-168125). 19 of the publication, those shown in FIGS. 1 and 5 of JP 2012-89102 A, OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP 2 of Japanese Patent Laid-Open No. 2013-54727), other configurations (for example, the one shown in FIG. 6 of Japanese Patent Laid-Open No. 2013-164871), various out-cell types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.).
Examples of the touch panel according to the present disclosure include those described in paragraph 0229 of JP-A-2017-120345.

The embodiment of the present invention will be described more specifically with reference to the following examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the following specific examples. In addition, "part" and "%" are based on mass unless otherwise specified.

[Polymer in positive photosensitive resin layer]
In the examples below, the following abbreviations respectively represent the following compounds:
ATHF: 2-tetrahydrofuranyl acrylate (synthetic product)
MATHF: 2-Tetrahydrofuranyl methacrylate (synthetic product)
AA: Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
MMA: Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
EA: Ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
CHA: cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
PGMEA (Propylene glycol monomethyl ether acetate): (Showa Denko KK)
V-601: Dimethyl 2,2'-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

<Synthesis of ATHF>
It was synthesized according to the method described in paragraph 0166 of WO2018 / 179640.

<Synthesis of MATHF>
It synthesize | combined according to the method of the paragraph 0167 of international publication 2018/179640.

<Synthesis Example of Polymer A-1>
PGMEA (75.0 parts) was put into a three-necked flask, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. ATHF (30.0 parts), MMA (35.0 parts), EA (35.0 parts), V-601 (4.0 parts), PGMEA (75.0 parts) was added to the solution at 90 ° C ± The solution was added dropwise to the three-necked flask solution maintained at 2 ° C over 2 hours. After the dropping was completed, the mixture was stirred at 90 ° C. ± 2 ° C. for 2 hours to obtain a polymer A-1 (solid content concentration 40.0%). The Tg was 35 ° C. and the weight average molecular weight (Mw) was 35,000.

<Synthesis Example of Polymer A-2>
The monomer was changed to MATHF (40.0 parts), AA (3.0 parts) and CHA (57.0 parts), and the other conditions were the same as in A-1. The solid content concentration of the polymer was 40% by mass. The Tg was 48 ° C. and the weight average molecular weight (Mw) was 25,000.

<Synthesis Example of Polymer A-3>
Polymer A-3 (PHS-EVE having the following structure, weight average molecular weight: 20,000) was obtained according to the method described in paragraph 0232 of JP-A-2014-85643. In the following structure, the numerical value of each structural unit represents the content (mass%) of each structural unit.

[Photo acid generator]
B-1: Irgacure PAG-103 manufactured by BASF, the following compound

B-2: a compound having the structure shown below (a compound described in paragraph 0227 of JP 2013-47765 A, which was synthesized according to the method described in paragraph 0227)

[Surfactant]
E-1: Compound having the structure shown below

[Basic compound]
D-1: N-cyclohexyl-N '-[2- (4-morpholinyl) ethyl] thiourea (manufactured by Toyo Kasei Co., Ltd., product number: CMTU)

<Preparation of Photosensitive Resin Composition 1>
Photosensitive resin composition 1 was obtained by blending with the following composition and filtering with a filter made of polytetrafluoroethylene having a pore size of 0.2 μm.

[Composition of Photosensitive Resin Composition 1]
PGMEA: 424.5 parts by mass Polymer A-1: 237.0 parts by mass Photoacid generator B-2: 5.0 parts by mass Surfactant E-1: 0.1 parts by mass Basic compound D-1: 0.1 parts by mass

<Preparation of Composition 1 for Forming Intermediate Layer>
Each component was mixed in the following composition to prepare a composition 1 for forming an intermediate layer.

[Composition of Composition 1 for Forming Intermediate Layer]
-Pure water: 33.7 parts by mass-Methanol: 61.2 parts by mass-Hydroxypropyl cellulose (HPC, HPC-SSL manufactured by Nippon Soda Co., Ltd.): 5.0 parts by mass-Megafuck F-569 (F-569) Manufactured by DIC Co., Ltd., including fluorine atom-containing nonionic surfactant (oligomer) having a molecular weight of 700 or more.): 0.1 part by mass

[Preparation of Compositions 2 to 16 for Forming Intermediate Layer]
Preparation of the intermediate layer forming composition 1 except that the types of the water-soluble resin and the surfactant in the intermediate layer forming composition 1 and the addition amount of the surfactant were changed as described in Table 1 below. By the same method, intermediate layer forming compositions 2 to 16 were prepared.

All the surfactants listed in Table 1 were dissolved in 100 g of distilled water at 25 ° C. in an amount of 1.0 g or more.
Further, details of the abbreviations described in Table 1 other than the above are shown below.
HPMC: Hydroxypropyl methylcellulose, TC-5E low molecular weight type manufactured by Shin-Etsu Chemical Co., Ltd. F-114: Megafac F-114, manufactured by DIC Corporation, an anionic surfactant having a perfluoroalkyl group and a sulfonic acid group. , Those having a molecular weight of 700 or more are not included.
F-410: Megafac F-410, manufactured by DIC Corporation, does not include anionic surfactant having a perfluoroalkyl group and a carboxy group and having a molecular weight of 700 or more.
F-444: Megafac F-444, manufactured by DIC Corporation, does not include a nonionic surfactant having a perfluoroalkyl group and an alkyleneoxy group and having a molecular weight of 700 or more.
F-477: Megafac F-477, manufactured by DIC Corporation, including a nonionic surfactant (oligomer) having a fluorine atom and having a molecular weight of 700 or more.
F-510: Megafac F-510, manufactured by DIC Corporation, including an anionic surfactant (oligomer) having a perfluoroalkyl group and a phosphoric acid group, having a molecular weight of 700 or more.
F-553: Includes Megafac F-553, manufactured by DIC Corporation, a nonionic surfactant (oligomer) having a fluorine atom, and having a molecular weight of 700 or more.
F-556: Megafac F-556, manufactured by DIC Corporation, including a fluorine atom-containing nonionic surfactant (oligomer) having a molecular weight of 700 or more.
F-559: Megafac F-556, manufactured by DIC Corporation, including a nonionic surfactant (oligomer) having a fluorine atom and having a molecular weight of 700 or more.
R-94: Megafac R-94, manufactured by DIC Corporation, including a nonionic surfactant (oligomer) having a fluorine atom and having a molecular weight of 700 or more.

(Example 1)
<Preparation of transfer material>
Onto a polyethylene terephthalate (PET) film (temporary support, thickness: 25 μm), the above composition 1 for forming an intermediate layer was applied in an amount such that the dry film thickness was 1.6 μm using a slit nozzle. After the composition 1 for forming an intermediate layer was dried, the composition 1 for forming an intermediate layer was further applied thereon by an amount of 0.4 μm using a slit nozzle.
After drying the composition 1 for forming an intermediate layer, the photosensitive resin composition 1 was applied thereon in an amount such that the dry film thickness was 3.0 μm.
Then, it was dried with warm air at 100 ° C., and finally a polyethylene film (OSM-N, manufactured by Tredegar Co., Ltd.) was pressure-bonded as a cover film to prepare a transfer material (photosensitive transfer material) of Example 1.

(Examples 2 to 14)
Transfer materials of Examples 2 to 14 were prepared in the same manner as in Example 1 except that the composition 1 for forming an intermediate layer was changed to the composition 2 for forming an intermediate layer to the composition 14 for forming an intermediate layer.

(Example 15)
The composition 4 for forming an intermediate layer was applied onto a PET film (temporary support, thickness: 25 μm) using a slit-shaped nozzle in an amount such that the dry film thickness was 1.6 μm. After the composition 4 for forming an intermediate layer was dried, the composition 15 for forming an intermediate layer was further applied thereon by an amount of 0.4 μm using a slit nozzle.
After drying the composition 15 for forming the intermediate layer, the photosensitive resin composition 1 was applied thereon in an amount such that the dry film thickness was 3.0 μm.
Then, it was dried with warm air of 100 ° C., and finally a polyethylene film (OSM-N, manufactured by Tredegar Co., Ltd.) was pressure-bonded as a cover film to prepare a transfer material of Example 15.

(Example 16)
A transfer material of Example 16 was produced in the same manner as in Example 1 except that the dry film thickness of the photosensitive resin composition 1 was applied in an amount of 5.0 μm.

(Examples 17 and 18)
A transfer material of Example 17 or Example 18 was produced in the same manner as in Example 1 except that the photosensitive resin composition 1 was changed to the photosensitive resin composition 2 or the photosensitive resin composition 3.

<Preparation of Photosensitive Resin Compositions 2 and 3>
Photosensitive resin compositions 2 and 3 were obtained by blending with the following composition and filtering with a filter made of polytetrafluoroethylene having a pore size of 0.2 μm.

[Composition of Photosensitive Resin Composition 2]
PGMEA: 424.5 parts by mass Polymer A-2: 237.0 parts by mass Photoacid generator B-2: 5.0 parts by mass Surfactant E-1: 0.1 parts by mass Basic compound D-1: 0.1 parts by mass

[Composition of Photosensitive Resin Composition 3]
PGMEA: 424.5 parts by mass Polymer A-3: 237.0 parts by mass Photoacid generator B-1: 5.0 parts by mass Surfactant E-1: 0.1 parts by mass Basic compound D-1: 0.1 parts by mass

(Example 19)
<Preparation of transfer material>
The composition 1 for forming an intermediate layer was applied onto PET using a slit-shaped nozzle in an amount such that the dry film thickness was 1.6 μm.
After drying the composition 1 for forming an intermediate layer, the photosensitive resin composition 1 was applied thereon in an amount such that the dry film thickness was 3.0 μm.
Then, it was dried with warm air of 100 ° C., and finally a polyethylene film (OSM-N, manufactured by Tredegar Co., Ltd.) was pressure-bonded as a cover film to prepare a transfer material of Example 19.

(Comparative Example 1)
A transfer material of Comparative Example 1 was produced in the same manner as in Example 1 except that the composition 1 for forming an intermediate layer was changed to the composition 16 for forming an intermediate layer.

<Strip evaluation>
The cover film was peeled off from the produced transfer material, the light of a fluorescent lamp was applied to the transfer material, and the appearance of the streaks was evaluated visually at an angle of 45 °. The “streaks” in the transfer material according to the present disclosure are stripes on the surface to be transferred in the transfer material (transfer surface, in the above-described Examples and Comparative Examples, the surface of the photosensitive resin layer from which the cover film has been peeled off). Indicates a failure that causes unevenness. In many cases, the streaks are generated in parallel with the conveying direction when the transfer material is manufactured. When the above-mentioned streaks are generated, bubbles often enter the streaks when transferred, and defects in the pattern shape (pattern omission, pattern collapse, etc.) and transfer as an etching resist for making circuit wiring When a material is used, many wiring defects are likely to occur.
It is preferably A or B, and more preferably A.
-Evaluation criteria-
A: No streak is visible when observed from a distance of 15 cm or 40 cm.
B: Streaks are not visible when observed from a distance of 40 cm, but streaks are visible when observed from a distance of 15 cm.
C: Streaks are clearly visible when observed from a distance of 15 cm or 40 cm.

<Evaluation of wiring defects>
-Substrate fabrication-
A roll-shaped substrate (PET substrate with a copper layer) was prepared by forming a copper layer on a polyethylene terephthalate (PET) film having a thickness of 200 μm with a thickness of 250 nm by a sputtering method.

-Evaluation of wiring defects-
The cover film was peeled from the produced transfer material, and laminated on a PET substrate with a copper layer under laminating conditions of a laminating roll temperature of 100 ° C., a linear pressure of 0.6 MPa, and a linear velocity (laminating speed) of 4.0 m / min. A line-and-space pattern (Duty ratio 1: 1) mask having a line width of 6 μm was brought into contact with a temporary support, exposed by an ultra-high pressure mercury lamp, left at 23 ° C. for 3 hours, and then developed. The development was carried out for 40 seconds by shower development using a 1.0% by mass sodium carbonate aqueous solution at 28 ° C. A line-and-space pattern having a line width of 6 μm was formed by the above method, and the exposure amount at which the ratio of the line width to the space width was 1: 1 was determined. A line-and-space pattern having a line width of 6 μm at the exposure amount was formed by the above method, and etching was performed by immersing in a copper etching solution (Cu-02, manufactured by Kanto Kagaku Co., Ltd.) at 25 ° C. for 5 minutes to form a square shape. The copper pattern wiring of was produced. The obtained copper pattern wiring was observed with an optical microscope. The observation area of 0.26 mm × 0.20 mm in the copper pattern wiring was taken as one shot, and the number of wiring defects of the copper pattern wiring was measured in a total of 5 shots at the central portion of the copper pattern wiring and the four corners of the square shape. Among the five shots, the following evaluation was performed by the maximum number of the total number of wiring defects of disconnection (open) of wiring and coupling (short) of wiring in one shot. It is preferably A or B.
A: No defects of the copper pattern are visually recognized.
B: The number of defects in the copper pattern is 1 or more and 4 or less.
C: The number of defects in the copper pattern is 5 or more.

<Adhesion evaluation>
The cover film was peeled off from the produced transfer material, and laminated on the PET substrate with a copper layer under the laminating conditions of a laminating roll temperature of 100 ° C., a linear pressure of 0.6 MPa, and a linear velocity (laminating speed) of 4.0 m / min. Next, a sample was prepared by cutting into 4.5 cm × 10 cm, and the PET substrate side with the copper layer was fixed on a sample table.
Using a tensile compression tester (SV-55 manufactured by Imada Seisakusho Co., Ltd.), the PET substrate with the copper layer was pulled in a direction of 180 degrees at 5.5 mm / sec to form an intermediate layer and a temporary support. It peeled between and measured the adhesive force.
The measured adhesive force (N / cm) was used as an index of adhesiveness and evaluated according to the following evaluation criteria. It can be said that the greater the adhesion, the better the adhesion. The evaluation results are shown in Table 2.
-Evaluation criteria-
A: Adhesion exceeds 0.098 N / cm.
B: The adhesion is 0.069 N / cm to 0.098 N / cm.
C: Adhesion is less than 0.069 N / cm.

It can be seen from Table 2 above that the transfer materials of Examples 1 to 19 have less streaks on the surface to be transferred than the transfer materials of Comparative Example 1.
Further, from Table 2 above, the transfer materials of Examples 1 to 19 are excellent in adhesion in transfer, and there are few wiring defects when the transfer material is used as an etching resist.

(Example 101)
On a PET substrate having a thickness of 100 μm, ITO was deposited as a second conductive layer to a thickness of 150 nm by sputtering, and copper was deposited thereon as a first conductive layer to a thickness of 200 nm by a vacuum deposition method. And used as a circuit forming substrate.
The transfer material obtained in Example 1 was attached to the substrate on the copper layer (laminating roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.) To obtain a laminate. A photomask provided with a pattern (hereinafter, also referred to as “pattern A”) shown in FIG. 2 having a structure in which conductive layer pads are connected in one direction without peeling off the temporary support is obtained. The contact pattern was exposed by using.
In the pattern A shown in FIG. 2, the solid line portion SL and the gray portion G are light-shielding portions, and the dotted line portion DL virtually shows a frame for alignment alignment.
Thereafter, the temporary support was peeled off, and development and washing were carried out to obtain pattern A. Then, after etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Inc.), the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.). A substrate in which both copper and ITO were drawn in the pattern A was obtained.
Next, in alignment, pattern exposure was performed using a photomask provided with openings of the pattern shown in FIG. 3 (hereinafter, also referred to as “pattern B”), and development and washing were performed.
In the pattern B shown in FIG. 3, the gray part G is a light-shielding part, and the dotted line part DL is a virtual frame for alignment.
Then, the copper layer was etched using Cu-02, and the remaining photosensitive resin layer was stripped using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
When the obtained circuit wiring board was observed with a microscope, there was no peeling or chipping, and it was a clean pattern.

(Example 102)
On a PET substrate having a thickness of 100 μm, ITO was deposited as a second conductive layer to a thickness of 150 nm by sputtering, and copper was deposited thereon as a first conductive layer to a thickness of 200 nm by a vacuum deposition method. And used as a circuit formation substrate.
The transfer material obtained in Example 1 was attached to the substrate on the copper layer (laminating roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.) To obtain a laminate. The obtained laminated body was pattern-exposed using a photomask provided with a pattern A having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support. Thereafter, the temporary support was peeled off, and development and washing were carried out to obtain pattern A. Then, after etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Inc.), the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.). A substrate in which both copper and ITO were drawn in the pattern A was obtained.
Then, PET (A) was laminated as a protective layer on the remaining resist. In this state, pattern exposure was performed using a photomask provided with openings for the pattern B in alignment with each other, and the PET (A) was peeled off, followed by development and washing with water. Then, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
When the obtained circuit wiring board was observed with a microscope, there was no peeling or chipping, and it was a clean pattern.

(Example 103)
On a 100 μm-thick cycloolefin polymer (COP) substrate, ITO was deposited as a second conductive layer to a thickness of 150 nm by sputtering, and copper was deposited thereon as a first conductive layer to a thickness of 200 nm by a vacuum deposition method. To form a substrate for forming a conductive pattern.
The transfer material obtained in Example 1 was attached to the substrate on the copper layer (laminating roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.) To obtain a laminate. The obtained laminated body was pattern-exposed using a photomask provided with a pattern A having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support. After that, the temporary support was peeled off, developed and washed with water to obtain a resin pattern drawn with pattern A. Then, after etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Inc.), the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.) By peeling using (KP-301 manufactured by Kanto Chemical Co., Inc.), a substrate in which both copper and ITO were drawn in the pattern A was obtained.
Then, the transfer material obtained in Example 1 was bonded onto the remaining resist (roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.). In this state, pattern alignment was performed using a photomask provided with an opening for the pattern B, and the temporary support of the transfer material was peeled off, followed by development and washing with water. Then, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board having a conductive pattern. ..
When the obtained circuit wiring board was observed with a microscope, there was no peeling or chipping, and it was a clean pattern.

The disclosure of Japanese Patent Application No. 2018-217753 filed on Nov. 20, 2018 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference. Are incorporated herein by reference.

10: temporary support, 12: intermediate layer, 14: photosensitive resin layer, 16: cover film, 100: transfer material, SL: solid line part, G: gray part, DL: dotted line part

Claims

A temporary support,
An intermediate layer containing a water-soluble resin,
Having a positive photosensitive resin layer, in this order,
The transfer material, wherein the intermediate layer contains a surfactant having a fluorine atom.
The transfer material according to claim 1, wherein the surfactant contains a compound having a molecular weight of 700 or more.
The transfer material according to claim 1 or 2, wherein the solubility of the surfactant in 100 g of water at 25 ° C is 1 g or more.
The transfer material according to any one of claims 1 to 3, wherein the content of the surfactant is 0.1% by mass to 1.0% by mass with respect to the total mass of the intermediate layer.
The transfer material according to any one of claims 1 to 4, wherein the surfactant is a surfactant having a fluoroalkyl group and an alkyleneoxy group.
The transfer material according to any one of claims 1 to 5, wherein the surfactant is a surfactant having a perfluoroalkyl group and a polyalkyleneoxy group.
7. The content of the polymer component in the positive photosensitive resin layer is 75% by mass or more based on the total mass of the positive photosensitive resin layer, according to any one of claims 1 to 6. Transfer material.
8. The positive type photosensitive resin layer according to claim 1, wherein the positive type photosensitive resin layer contains a polymer containing a structural unit having an acid group protected by an acid-decomposable group, and a photo-acid generator. The transfer material described.
9. The transfer material according to claim 8, wherein the structural unit having an acid group protected by an acid-decomposable group is a structural unit represented by any one of the following formulas A1 to A3.

In formula A1, R 11 and R 12 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 11 and R 12 is an alkyl group or an aryl group, and R 13 is an alkyl group or It represents an aryl group, R 11 or R 12 and R 13 may be linked to form a cyclic ether, R 14 is a hydrogen atom or a methyl group, and X 1 is a single bond or a divalent linking group. R 15 represents a substituent, and n represents an integer of 0 to 4.
In formula A2, R 21 and R 22 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 21 and R 22 is an alkyl group or an aryl group, and R 23 is an alkyl group or It represents an aryl group, and R 21 or R 22 and R 23 may be linked to form a cyclic ether, and R 24 is independently a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, It represents 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 formula A3, R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group or It represents an aryl group, R 31 or R 32 and R 33 may be linked to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or a divalent linking group. Represents.
A step of bringing the outermost layer of the transfer material according to any one of claims 1 to 9 on the side having the positive photosensitive resin layer into contact with the temporary support, and bonding the substrate to the temporary support;
A step of pattern-exposing the positive photosensitive resin layer,
And a step of developing the exposed positive photosensitive resin layer to form a resin pattern in this order.
The outermost layer on the side having the positive photosensitive resin layer with respect to the temporary support in the transfer material according to any one of claims 1 to 9 is brought into contact with a substrate having a conductive layer to be attached. The process of matching
A step of pattern-exposing the positive photosensitive resin layer,
A step of developing the exposed positive photosensitive resin layer to form a resin pattern,
And a step of etching the conductive layer in a region where the resin pattern is not arranged, in this order.
The outermost layer on the side having the positive photosensitive resin layer with respect to the temporary support in the transfer material according to any one of claims 1 to 9 is brought into contact with a substrate having a conductive layer to be attached. The process of matching
A step of pattern-exposing the positive photosensitive resin layer,
A step of developing the exposed positive photosensitive resin layer to form a resin pattern,
And a step of etching the conductive layer in a region where the resin pattern is not arranged, in this order.