CN111684359A

CN111684359A - Photosensitive transfer material, method for manufacturing circuit wiring, and method for manufacturing touch panel

Info

Publication number: CN111684359A
Application number: CN201980011644.1A
Authority: CN
Inventors: 山田悟; 松田知树; 藤本进二; 筱田克己; 石坂壮二; 汉那慎一; 两角一真
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2018-02-05
Filing date: 2019-02-05
Publication date: 2020-09-18
Also published as: TW201938384A

Abstract

A photosensitive transfer material, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel, comprising a temporary support, an intermediate layer, and a resist layer in this order, the intermediate layer containing a component (A): a dye which has a maximum absorption wavelength of 450nm or more in a wavelength range of 400 to 780nm during color development and in which the maximum absorption wavelength is changed by an acid, an alkali or a radical.

Description

Photosensitive transfer material, method for manufacturing circuit wiring, and method for manufacturing touch panel

Technical Field

The present invention relates to a photosensitive transfer material, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel.

Background

In a display device (such as an organic Electroluminescence (EL) display device and a liquid crystal display device) including a touch panel such as a capacitive input device, a conductive layer pattern such as an electrode pattern of a sensor corresponding to a visual recognition unit, a wiring line in an edge wiring portion and a wiring line in a lead-out wiring portion is provided inside the touch panel.

In general, when a patterned layer is formed, since the number of steps for obtaining a desired pattern shape is small, a method of exposing a resist layer provided on an arbitrary substrate using a photosensitive transfer material through a mask having a desired pattern and then developing the resist layer is widely used.

Further, as a conventional resist layer composition and photosensitive transfer material, a resist layer composition and a photosensitive transfer material described in japanese patent laid-open nos. 2008-064908, 2004-054106, 2009-003000, and 2002-341544 are known. A photosensitive transfer material having a support, a dye-containing buffer layer, and a photosensitive layer is also disclosed (for example, japanese patent application laid-open No. 2006-085116).

As a metal film-attached thin film used for manufacturing a conventional circuit board, a thin film described in japanese patent application laid-open No. 2011-025532 is known.

Jp 2011-025532 a discloses a metal film-coated film comprising a support, a water-soluble polymer release layer containing a nano inorganic filler formed on the support, and a metal film layer formed on the release layer.

Disclosure of Invention

Technical problem to be solved by the invention

An object to be solved by one embodiment of the present invention is to provide a photosensitive transfer material having excellent visibility of an exposed portion and an unexposed portion.

Another object of another embodiment of the present invention is to provide a method for manufacturing a circuit wiring or a method for manufacturing a touch panel using the photosensitive transfer material.

Means for solving the technical problem

Means for solving the above problems include the following means.

< 1 > a photosensitive transfer material comprising a temporary support, an intermediate layer and a resist layer in this order, wherein the intermediate layer contains the following component (A).

(A) The components: a dye having a maximum absorption wavelength of 450nm or more in a wavelength range of 400 to 780nm during color development and a maximum absorption wavelength that changes with an acid, an alkali or a radical

< 2 > the photosensitive transfer material according to < 1 >, wherein,

the coloring matter as the component (A) is a pH sensitive coloring matter.

< 3 > the photosensitive transfer material according to < 1 > or < 2 >, wherein,

the colorant as the component (A) has a triarylmethane skeleton.

< 4 > the photosensitive transfer material according to any one of < 1 > -3 >, wherein,

the dye as component (A) contains at least 1 selected from the group consisting of a dye represented by formula I, an open ring body of a dye represented by formula I, and a neutralizer of the open ring body.

[ chemical formula 1]

In the formula I, Ar and Ar' independently represent an aromatic group. R¹、R²、R³And R⁴Each independently represents a hydrogen atom or a substituent having a valence of 1.

< 5 > the photosensitive transfer material according to any one of < 1 > -4 >, wherein,

The resist layer contains the following components (B) and (C).

(B) The components: polymer containing structural unit having acid group protected by acid-decomposable group

(C) The components: photoacid generators

< 6 > the photosensitive transfer material according to < 5 >, wherein,

the maximum absorption wavelength in the wavelength range of 400nm to 780nm in the color development of the dye as the component (A) is changed by an acid emitted from the photoacid generator as the component (C) by exposure.

< 7 > the photosensitive transfer material according to < 6 >, wherein,

the maximum absorption wavelength in the wavelength range of 400nm to 780nm in the color development of the dye as the component (A) is shortened by the acid emitted from the photoacid generator (C) by exposure.

< 8 > the photosensitive transfer material according to any one of < 5 > -7 >, wherein,

the acid generated from the photoacid generator as component (C) is phosphoric acid or sulfonic acid, and has a pKa of 4 or less.

< 9 > the photosensitive transfer material according to any one of < 5 > - < 8 >, wherein,

the structural unit having a group in which an acid group is protected with an acid-decomposable group, which the polymer as the component (B) has, is a structural unit represented by the following formula II.

[ chemical formula 2]

In the formula II, R¹And R²Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R¹And R²Any of which is alkyl or aryl, R³Represents alkyl or aryl, R¹Or R²And R³May be linked to form a cyclic ether. R⁴Represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group.

< 10 > the photosensitive transfer material according to any one of < 1 > - < 9 >, wherein,

the intermediate layer further contains the following component (G).

(G) The components: pH regulator

< 11 > the photosensitive transfer material according to < 10 >, wherein,

the pH regulator is quaternary ammonium salt.

< 12 > the photosensitive transfer material according to any one of < 1 > -11 >, wherein,

the resist layer further contains the following component (D).

(D) The components: basic compound

< 13 > a method for manufacturing a circuit wiring, which comprises, in order:

bonding the photosensitive transfer material of any one of < 1 > -to < 12 > to a substrate so that a resist layer of the photosensitive transfer material is in contact with the substrate; a step of pattern-exposing the resist layer of the photosensitive transfer material after the step of bonding; a step of forming a pattern by developing the resist layer after the step of exposing the pattern; and a step of etching the substrate in the region where no pattern is disposed.

< 14 > a method for manufacturing a touch panel, comprising in order:

< 2-1 > a photosensitive transfer material comprising a temporary support, an intermediate layer and a photosensitive resin layer in this order, wherein the intermediate layer comprises a water-soluble resin, particles and a polar compound having at least 1 polar group selected from the group consisting of an acidic group, a basic group, an anionic group and a cationic group and an alkyl group having 6 or more carbon atoms, the photosensitive resin layer comprises a polymer containing a structural unit having an acid group protected by an acid-decomposable group, and the photosensitive resin layer is in contact with the intermediate layer.

< 2-2 > the photosensitive transfer material according to < 2-1 > wherein,

The acid value of the polymer is 10mgKOH/g or less.

< 2-3 > the photosensitive transfer material according to < 2-1 > or < 2-2 >, wherein,

the acid value of the polymer is 3mgKOH/g or less.

< 2-4 > the photosensitive transfer material according to any one of < 2-1 > - < 2-3 >, wherein,

the polar group is a primary to tertiary amino group or a primary to quaternary ammonium group.

< 2-5 > the photosensitive transfer material according to any one of < 2-1 > - < 2-4 >, wherein,

the alkyl group having 6 or more carbon atoms in the polar compound is an alkyl group having 10 to 16 carbon atoms.

< 2-6 > the photosensitive transfer material according to any one of < 2-1 > - < 2-5 >, wherein,

the particles are silica particles.

< 2-7 > the photosensitive transfer material according to < 2-6 >, wherein,

the silica particles are silica particles having an anionic group on the surface.

< 2-8 > the photosensitive transfer material according to any one of < 2-1 > - < 2-7 >, wherein,

the arithmetic mean particle diameter of the particles is 30nm or less.

< 2-9 > the photosensitive transfer material according to any one of < 2-1 > - < 2-8 >, wherein,

a water-soluble resin layer having a particle content of 5 mass% or less is further provided between the temporary support and the intermediate layer.

< 2-10 > a method for manufacturing a resin pattern, which comprises, in order:

a step of bonding the photosensitive resin layer of the photosensitive transfer material of any one of < 2-1 > < 2-9 > to a substrate by bringing the photosensitive resin layer into contact with the substrate; a step of pattern-exposing the photosensitive resin layer; and a step of forming a pattern by developing the exposed photosensitive resin layer.

< 2-11 > a method for manufacturing a circuit wiring, which comprises, in order:

a step of bonding the photosensitive resin layer of the photosensitive transfer material of any one of < 2-1 > - < 2-9 > to a substrate having a conductive layer in contact therewith; a step of pattern-exposing the photosensitive resin layer; a step of forming a pattern by developing the exposed photosensitive resin layer; and a step of etching the conductive layer in the region where the pattern is not arranged.

< 2-12 > a method for manufacturing a touch panel, comprising in order:

Effects of the invention

According to one embodiment of the present invention, a photosensitive transfer material having excellent visibility of an exposed portion and an unexposed portion can be provided.

Further, according to another embodiment of the present invention, a method for manufacturing a circuit wiring and a method for manufacturing a touch panel using the photosensitive transfer material can be provided.

Drawings

Fig. 1 is a schematic view showing an example of the layer structure of the photosensitive transfer material according to the present invention.

Fig. 2 is a schematic view showing an example of a method for manufacturing a circuit wiring for a touch panel using the photosensitive transfer material according to the present invention.

Fig. 3 is a schematic view showing pattern a.

Fig. 4 is a schematic view showing pattern B.

Detailed Description

The present invention will be described below. Note that, although the description is made with reference to the drawings, the reference numerals may be omitted.

In the present invention, the numerical range represented by the term "to" means a range in which the numerical values before and after the term "to" are included as the lower limit value and the upper limit value. In the numerical ranges recited in the present invention, the upper limit or the lower limit recited in one numerical range may be replaced with the upper limit or the lower limit recited in another numerical range recited in a stepwise manner. In the numerical ranges described in the present invention, the upper limit or the lower limit described in a certain numerical range may be replaced with the values shown in the examples.

In the present invention, "(meth) acrylic acid" represents both or either of acrylic acid and methacrylic acid, and "(meth) acrylate" represents both or either of acrylate and methacrylate.

In the present invention, the amount of each component in the composition refers to the total amount of a plurality of substances present in the composition, unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition.

In the present invention, the term "step" includes not only an independent step but also a step that can achieve the intended purpose of the step even when the step cannot be clearly distinguished from other steps.

In the labeling of the group (atomic group) in the present invention, the unsubstituted and substituted labels include those having a substituent as well as those having no substituent. For example, "alkyl" means that an alkyl group having a substituent (substituted alkyl) is included as well as an alkyl group having no substituent (unsubstituted alkyl).

The chemical structural formula in the present invention may be described by a simplified structural formula in which a hydrogen atom is omitted.

In the present invention, "mass%" means the same as "weight%" and "parts by mass" means the same as "parts by weight".

In the present invention, a combination of preferred embodiments of 2 or more is a more preferred embodiment.

In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are molecular weights converted using polystyrene as a standard substance, which are detected by a solvent THF (tetrahydrofuran) or a differential refractometer using a Gel Permeation Chromatography (GPC) analyzer using a column using TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both product names manufactured by tosohcorroporation), unless otherwise specified.

(photosensitive transfer Material)

(embodiment 1 of photosensitive transfer Material)

In embodiment 1 of the photosensitive transfer material according to the present invention, the intermediate layer and the resist layer are provided in this order on the temporary support, and the intermediate layer contains a dye having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm during color development and a maximum absorption wavelength that changes by an acid, an alkali, or a radical as the component (a).

The problems and effects described above are the problems and effects in embodiment 1 of the photosensitive transfer material according to the present invention.

From the viewpoint of checking the exposed portion, the photosensitive transfer material as the dry film resist is required to have visibility of the exposed portion. In order to impart visibility, it is known to introduce a developer into a resist layer, but there is a concern about various adverse effects. The present inventors have found that a photosensitive transfer material in which a color developing mechanism is introduced into an intermediate layer instead of a resist layer to reduce various adverse effects can be provided.

As a result of intensive studies, the present inventors have found that a photosensitive transfer material having the above-described structure can provide a photosensitive transfer material having excellent visibility of exposed portions and unexposed portions.

The photosensitive transfer material of the present invention can suppress the occurrence of coloring or discoloring of a dye in an unexposed portion and can cause coloring or discoloring of a dye only in an exposed portion when exposed to light. As a result, it is estimated that the portion where the coloration or the discoloration is generated is easily visually distinguished from the portion where the coloration or the discoloration is not generated, and excellent visibility can be obtained.

From the above viewpoint, it is preferable to include a material (for example, a photoacid generator described later) which promotes color development or decolorization of the dye as the component (a) by exposure.

The photosensitive transfer material in the present invention may be a so-called negative photosensitive transfer material in which the removability in development is decreased by exposure, or a so-called positive photosensitive transfer material in which the removability in development is increased by exposure.

In the case of a positive photosensitive transfer material, the photosensitive transfer material is preferably a chemically amplified positive photosensitive transfer material.

The photosensitive transfer material according to the present invention can be an NQD-based photosensitive transfer material using NQD (naphthoquinone diazide).

As the naphthoquinone diazide, for example, naphthoquinone diazide described in paragraph 0201 of Japanese patent laid-open publication No. 2004-126047 can be used.

When the photosensitive transfer material of the present invention is an NQD-based photosensitive transfer material, it preferably contains a novolac resin.

As the novolak resin, for example, the novolak resin described in paragraph 0201 of japanese patent application laid-open No. 2004-126047 can be used.

The photosensitive transfer material according to embodiment 1 of the present invention will be described in detail below.

In addition, in the case where the photosensitive transfer material is simply referred to as "photosensitive transfer material" in a portion before the description of embodiment 2 of the photosensitive transfer material according to the present invention in the detailed description of the invention section below, it means "embodiment 1 of the photosensitive transfer material" unless otherwise specified.

[ intermediate layer ]

The intermediate layer according to the present invention contains a dye [ (A) component ] having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm during color development and a maximum absorption wavelength that changes by an acid, a base, or a radical. The intermediate layer is preferably a layer formed from the intermediate layer composition according to the present invention. The intermediate layer preferably contains the pigment according to the present invention.

As the intermediate layer, the intermediate layers described in paragraphs 0084 to 0087 of jp 2005-259138 a can be used. The intermediate layer is preferably dispersed or dissolved in water or an alkaline aqueous solution.

< pigment [ (component (A) ]

The intermediate layer of the photosensitive transfer material according to the present invention contains a dye which has a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm during color development and in which the maximum absorption wavelength is changed by an acid, an alkali, or a radical.

The "change in the maximum absorption wavelength by an acid, an alkali, or a radical" in the coloring matter may be any of a method in which a coloring matter in a colored state is decolored by an acid, an alkali, or a radical, a method in which a coloring matter in a decolored state is colored by an acid, an alkali, or a radical, and a method in which a coloring matter in a colored state is changed to a colored state of another color.

Specifically, the dye may be a compound that develops color by changing from a decolored state by exposure, or may be a compound that develops color by changing from a colored state by exposure. In this case, the dye may be one in which the state of color development or decoloration changes when an acid, a base, or a radical is introduced into the composition by exposure, or may be one in which the state of color development or decoloration changes when a property (for example, pH) in the system changes by introduction of an acid, a base, or a radical. Further, the dye may be one which is not exposed to light and is changed in a state in which an acid, a base, or a radical is directly supplied as a stimulus to develop or decolor.

Among them, from the viewpoint of visibility, a compound which is decolorized by exposure is preferable, and a latent pigment which is decolorized by an acid generated from a photoacid generator, that is, a pH sensitive pigment whose pH is decolorized by the generation of an acid is more preferable.

The pH sensitive dye was confirmed by the following method.

0.1g of a dye was dissolved in 100mL of a mixed solution of ethanol and water (ethanol/water: 1/2[ mass ratio ]), and 0.1mol/l (1N) of a hydrochloric acid aqueous solution was added thereto to adjust the pH to 1. Titration was carried out with 0.01mol/l (0.01N) aqueous sodium hydroxide solution, and a color development change and a pH at which the color development change was observed were confirmed. The pH was measured at 25 ℃ using a pH meter (model: HM-31, manufactured by DKK-TOACORPORATION).

As an example of the coloring mechanism of the dye in the present invention, the following mode can be obtained.

The intermediate layer is added with a photoacid generator, a photobase generator, or a photoradical generator, and after exposure, the acid-reactive dye, the base-reactive dye, or the radical-reactive dye (for example, a water-soluble leuco dye) is developed with an acid, a base, or a radical generated from the photoacid generator or the like.

In particular, in the case of a chemically amplified positive photosensitive transfer material, the following modes can be obtained.

A photoacid generator described later is added to the resist layer, and after exposure, the photoacid generator contained in the resist layer moves to the intermediate layer to generate an acid. Further, an acid-reactive dye (e.g., a water-soluble leuco dye) is developed by the generated acid.

The maximum absorption wavelength in the wavelength range of 400nm to 780nm in coloring of the dye is 450nm or more, and from the viewpoint of visibility, it is preferably 550nm or more, more preferably 550nm or more and 700nm or less, and still more preferably 550nm or more and 650nm or less.

The dye may have only 1 maximum absorption wavelength in the wavelength range of 400nm to 780nm in the case of color development, or may have 2 or more maximum absorption wavelengths in the wavelength range of 400nm to 780nm in the case of color development. When the dye has a maximum absorption wavelength in a wavelength range of 400nm to 780nm in the case of developing the color of 2 or more dyes, the maximum absorption wavelength in the case of developing the color with the highest absorbance among at least 1 maximum absorption wavelength in the case of developing the color of 2 or more dyes may be 450nm or more.

As for the measurement method of the maximum absorption wavelength, a spectrophotometer was used at 25 ℃ under an atmospheric atmosphere: UV3100 (manufactured by Shimadzu Corporation), a transmission spectrum was measured in a range of 400nm to 780nm, and the intensity of light was measured to be an extremely small wavelength (maximum absorption wavelength).

Examples of the coloring matter that develops color and discolors by exposure include colorless compounds.

Examples of the dye decolorized by exposure to light include a leuco compound, diarylmethane-based dye, oxazine-based dye, xanthene-based dye, iminonaphthoquinone-based dye, azomethine-based dye, and anthraquinone-based dye.

Among them, a colorless compound is preferable as the coloring matter from the viewpoint of visibility.

Examples of the colorless compound include colorless compounds such as triarylmethane-based (e.g., triphenylmethane-based), spiropyran-based, fluorescein-based, diarylmethane-based, rhodamine-based, indolylphthalein-based, and colorless auramine-based compounds. Among them, a colorless compound having a triarylmethane skeleton (triarylmethane-based coloring matter) is preferable, and a triphenylmethane-based coloring matter is more preferable.

The colorless compound preferably has a lactone ring, a sultone ring, or a sultone ring from the viewpoint of visibility. The colorless compound can have a lactone ring, a sultone ring, or a sultone ring, and can change to a closed ring state by reacting with an acid generated from a photoacid generator, for example, to discolor or change to a ring state by opening, thereby developing color. The compound having a lactone ring, a sultone ring or a sultone ring is preferable, and a colorless compound having a sultone ring and discolored by ring-closing of the sultone ring is more preferable.

The dye is preferably a water-soluble compound for the purpose of preventing defects caused by precipitation of the dye in the aqueous resist stripping liquid.

The pigment is water-soluble means that the amount of pigment dissolved is 0.1 part by mass or more (preferably 1 part by mass or more, more preferably 5 parts by mass or more) per 100 parts by mass of water at 25 ℃.

Among the above, from the viewpoint of visibility, it is preferable that the pigment contains at least 1 selected from the group consisting of a pigment represented by the following formula I, an open ring body of a pigment represented by the following formula I, and a neutralizer of the open ring body.

[ chemical formula 3]

In the formula (I), Ar and Ar' independently represent an aromatic group. R¹、R²、R³And R⁴Each independently represents a hydrogen atom or a substituent having a valence of 1.

Hereinafter, the closed ring body, the open ring body and the neutralizer of the open ring body of the dye of the present invention will be described by taking the compound A-1 as an example. The same applies to the other compounds represented by the formula (I).

The dye of the present invention is present in the intermediate layer in a state of equilibrium with a closed ring body, an open ring body, and a neutral body of the open ring body, as shown below, for example. For example, if the pH in the intermediate layer is acidic, the proportion of closed ring bodies present increases, and the proportion of open ring bodies and open ring body neutralizers present relatively decreases. Conversely, when the pH in the intermediate layer is alkaline, the ratio of the open ring bodies to the neutralizers of the open ring bodies increases, and the ratio of the closed ring bodies to the neutralizers relatively decreases.

In addition, since the closed ring body, the open ring body, and the neutralized body of the open ring body are different in color when they are developed, for example, when a photoacid generator is included in the intermediate layer, acid is released from the photoacid generator included in the intermediate layer in the exposed portion, and as a result, the pH of the exposed portion is decreased, and the color of the developed dye changes.

On the other hand, the color of the unexposed portion does not change. This enables good visibility of the exposed portion and the unexposed portion.

In the above equilibrium state, in order to adjust the pH in the intermediate layer and to adjust the presence ratio of the closed ring body, the open ring body, and the neutralized body of the open ring body, it is preferable to use a component (G) (NaOH or the like) which is a pH adjuster.

[ chemical formula 4]

The aromatic group in Ar and Ar' in the formula (I) may be an aryl group or a heteroaryl group, and may be a monocyclic aromatic group or a condensed ring in which 2 or more rings are condensed.

Ar and Ar' of the formula (I) may be bonded to form a ring. Further, Ar and Ar' are preferably a five-membered ring or a six-membered ring.

The aromatic group in Ar and Ar' of the formula (I) may have a substituent. Further, Ar and Ar' may have a plurality of the above substituents.

Examples of the substituent include a hydroxyl group, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamino group, an alkylarylamino group, and a diarylamino group, and a hydroxyl group, a halogen group, a dialkylamino group, an alkylarylamino group, and a diarylamino group are preferable.

The above-mentioned substituents can be bonded to at least 1 of the ortho-, meta-or para-positions. Preferably, the bond is bonded to at least 1 of the ortho-position or the para-position, and more preferably bonded to at least the para-position.

The halogen atom is preferably a bromine atom (Bromoatom) or an iodine atom, and more preferably a bromine atom (Bromoatom). The alkyl groups are preferably each independently an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.

These substituents may also be substituted by a substituent. Among them, Ar and Ar' are preferably a phenyl group having a hydroxyl group and a phenyl group substituted by a halogen atom.

From the viewpoint of sensitivity and visibility, the total number of carbon atoms of Ar and Ar' in formula (I) is preferably 4 to 50, more preferably 6 to 40, and still more preferably 10 to 30, independently.

R of the formula (I)¹、R²、R³And R⁴Examples thereof include a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamino group, an alkylarylamino group, a diarylamino group, and the like. Among them, a hydrogen atom is preferable.

Preferred specific examples of the coloring matter are compounds A-1 to A-15, but the coloring matter in the present invention is not limited thereto.

[ chemical formula 5]

[ chemical formula 6]

[ chemical formula 7]

The pigment may be used alone in 1 kind, or in 2 or more kinds.

The content of the coloring matter in the photosensitive transfer material according to the present invention is preferably 0.01 to 10% by mass, more preferably 0.1 to 8% by mass, and still more preferably 0.5 to 5% by mass, based on the total solid content of the intermediate layer composition, from the viewpoint of visibility.

In the present invention, the "solid component" in the intermediate layer composition means a component from which volatile components (for example, a solvent) are removed.

The content of the pigment is a content of the pigment in a case where the pigment contained in all the intermediate layer compositions is in a colored state. Hereinafter, a method for quantifying a dye in the case where the dye is a pH sensitive dye will be described.

The intermediate layer composition was prepared by dissolving 0.001g and 0.01g of the coloring matter contained in the intermediate layer composition in 100mL of a mixed solution of ethanol and water (ethanol/water 1/2[ mass ratio ]), adding 0.1mol/l (1N) aqueous hydrochloric acid to the mixture to prepare a pH of 1 or adding 0.01mol/l (0.01N) aqueous sodium hydroxide to the mixture to prepare a pH of 14, and then all the coloring matters were colored. Then, the absorbance was measured at 25 ℃ under an atmospheric atmosphere using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve was prepared.

Subsequently, absorbance was measured by the same method as described above except that 0.1g of the coloring matter was changed to 0.1g of the intermediate layer composition, and the pH was 1 or 14. Then, the amount of the pigment contained in the intermediate layer composition is calculated from a calibration curve prepared from the absorbance of the pigment and the absorbance of the intermediate layer composition.

< Polymer >

The intermediate layer can comprise a polymer.

The polymer used in the intermediate layer is preferably a water-soluble resin. Examples of the water-soluble resin include cellulose resins, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. Among them, cellulose resins are preferable, and hydroxypropyl cellulose and hydroxypropyl methyl cellulose are more preferable.

The water solubility of the polymer in the present invention means that the amount of the polymer dissolved in 100 parts by mass of water at 25 ℃ is 0.1 part by mass or more (preferably 1 part by mass or more, and more preferably 5 parts by mass or more).

From the viewpoint of adhesion, the content of the polymer in the photosensitive transfer material according to the present invention is preferably 20 to 100% by mass, and more preferably 50 to 100% by mass, based on the total solid content of the intermediate layer composition.

< surfactant >

From the viewpoint of film thickness uniformity, the intermediate layer preferably contains a surfactant. As the surfactant, any of anionic, cationic, Nonionic (Nonionic) and amphoteric surfactants can be used, but a preferred surfactant is a Nonionic surfactant.

The above is an example of the nonionic surfactant.

< inorganic Filler >

The intermediate layer may contain an inorganic filler. The inorganic filler in the present invention is not particularly limited. Examples thereof include silica particles, alumina particles, zirconia particles and the like, and silica particles are more preferable. From the viewpoint of transparency, particles having a small particle diameter are preferable, and particles having an average particle diameter of 100nm or less are more preferable. For example, as a commercially available product, SNOWTEX (registered trademark) is preferably used.

The volume fraction of the inorganic filler (the volume ratio of the particles in the intermediate layer) in the photosensitive transfer material according to the present invention is preferably 10 to 80% by mass, and more preferably 20 to 60% by mass, based on the total solid content of the intermediate layer composition, from the viewpoint of the adhesion between the intermediate layer and the photosensitive layer.

< pH adjuster [ (G) component ]

The intermediate layer can include a pH adjuster. By including the pH adjuster, the colored state or the decolored state of the dye in the composition can be maintained more stably, and the adhesion to the substrate can be further improved.

The pH adjuster in the present invention is not particularly limited. Examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, organic amines, organic ammonium salts and the like. From the viewpoint of water solubility, sodium hydroxide is preferred. From the viewpoint of adhesion between the resist layer and the intermediate layer, an organic ammonium salt is preferable.

Preferred examples of the organic ammonium salt include primary ammonium salts, secondary ammonium salts, tertiary ammonium salts, quaternary ammonium salts, and quaternary ammonium salts.

The quaternary ammonium salt may include tetraalkylammonium hydroxide which may have a substituent, and specific examples thereof include tetramethylammonium hydroxide, triethylmethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, hexadecyltrimethylammonium hydroxide, choline, benzyltrimethylammonium, benzyltriethylammonium, tris (2-hydroxyethyl) methylammonium hydroxide, and the like.

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. Examples of the substituent in the case of having a substituent include an aryl group having 6 to 12 carbon atoms (for example, a phenyl group), a hydroxyl group and the like.

The content of the pH adjuster in the photosensitive transfer material according to the present invention is preferably 1 to 50% by mass, and more preferably 3 to 30% by mass, based on the total solid content of the intermediate layer composition, from the viewpoint of stabilizing the color development state or the decolored state of the coloring matter.

< photoacid generators >

When the photosensitive transfer material in the present invention is a negative photosensitive transfer material, the intermediate layer may contain a photoacid generator. The photoacid generator is not particularly limited. These may be the same as the photoacid generator described later. The photoacid generator may be included in the intermediate layer composition and coated in advance, but may be included in the intermediate layer to cause diffusion when the resist layer composition is coated.

< photo radical generators >

In the case where the photosensitive transfer material in the present invention is a negative photosensitive transfer material, the photosensitive transfer material may contain a photo radical generator.

Examples of the photo-radical generator include dimethylaminoethyl aminobenzoate (DBE, CAS No.10287-53-3), benzoin methyl ether, anisyl group (p, p ' -dimethoxybenzyl), TAZ-110 (product name: Midori Kagaku Co., manufactured by Ltd.), benzophenone, TAZ-111 (product name: Midori Kagaku Co., manufactured by Ltd.), Irgacure OXE01, OXE02, OXE03 (manufactured by BASF Co., Ltd.), Omnirad651 and 369 (product name: IGM Resins B.V., manufactured by Ltd.), 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -bisimidazole (Tokyo Chemical Industry Co., manufactured by Ltd.), and the like.

Further, a photopolymerization initiator described later can also be used as the photo radical generator.

< photobase Generator >

In the case where the photosensitive transfer material in the present invention is a negative photosensitive transfer material, the photosensitive transfer material may contain a photobase generator.

Examples of the photobase generators include 2-nitrobenzylcyclohexylcyclohexylcarbamate, triphenylmethanol, o-carbamoylhydroxyamide, o-carbamoyloxime, [ [ (2, 6-dinitrobenzyl) oxy ] carbonyl ] cyclohexylamine, bis [ [ (2-nitrobenzyl) oxy ] carbonyl ] hexane 1, 6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaaminecobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, and mixtures thereof, 2, 6-dimethyl-3, 5-diacetyl-4- (2-nitrophenyl) -1, 4-dihydroxypyridine, 2, 6-dimethyl-3, 5-diacetyl-4- (2, 4-dinitrophenyl) -1, 4-dihydroxypyridine, and the like.

As an example of the thermokalite generator, a compound described in international publication No. 2015/199219 can be used.

Average film thickness of the intermediate layer-

The average film thickness of the intermediate layer is preferably 0.3 to 10 μm, more preferably 0.3 to 5 μm, and particularly preferably 0.3 to 2 μm, from the viewpoint of adhesion between the intermediate layer and the resist layer and pattern formability.

The method for measuring the average film thickness of each layer in the present invention is not particularly limited, and a known method can be used. Also, it is preferable to measure 10 or more points to calculate the average value.

Specifically, for example, surface shape measurement, cross-sectional observation with an optical microscope or an electron microscope, and the like can be given. In addition, Dektak series manufactured by Bruker can be preferably used for surface shape measurement. Also, a Scanning Electron Microscope (SEM) can be preferably used for cross-sectional observation.

Preferably, the thickness of the intermediate layer is smaller than the thickness of the resist layer.

The intermediate layer may have 2 or more layers.

When the intermediate layer has 2 or more layers, the average film thickness of each layer is not particularly limited as long as it is within the above range, but from the viewpoint of the adhesiveness between the intermediate layer and the resist layer and the pattern formability, the average film thickness of the layer closest to the resist layer among the 2 or more layers in the intermediate layer is preferably 0.3 to 10 μm, more preferably 0.3 to 5 μm, and particularly preferably 0.3 to 2.0 μm.

Method for forming intermediate layer

The intermediate layer composition for forming the intermediate layer can be prepared by mixing the respective components and the solvent at predetermined ratios by an arbitrary method and dissolving them with stirring. For example, the compositions can be prepared by dissolving the respective components in a solvent in advance, and then mixing the resulting solutions at a predetermined ratio. The composition prepared as above can also be used after being filtered with a filter having a pore size of 3.0 μm or the like.

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

[ resist layer ]

The resist layer according to the present invention is a layer which has photosensitivity and can be patterned by developing with a developer after exposure. The resist layer preferably contains a polymer containing a structural unit having a group in which an acid group is protected by an acid-decomposable group, and a photoacid generator. The resist layer is preferably a layer formed by the resist layer composition of the present invention.

The resist layer composition of the present invention is a chemically amplified positive resist layer from the viewpoint of high sensitivity.

< Polymer having structural Unit having acid group-protected group with acid-decomposable group [ (B) component ]

The resist layer composition according to the present invention may contain a polymer (also referred to as a "specific polymer") containing a structural unit (also referred to as a "structural unit b") having a group in which an acid group is protected with an acid-decomposable group.

The resist layer composition according to the present invention may contain other polymers in addition to the specific polymer having the structural unit b. In the present invention, the specific polymer having the structural unit b and other polymers are collectively referred to as "polymer components".

The specific polymer is subjected to deprotection reaction of the structural unit b having an acid group protected by acid decomposition in the specific polymer by the action of a catalytic amount of an acidic substance generated by exposure to light, thereby becoming an acid group. The acid group enables dissolution by development.

Preferred embodiments of the structural unit b are described below.

The specific polymer is preferably an addition polymerization type resin, and more preferably a polymer having a structural unit derived from (meth) acrylic acid or an ester thereof. In addition to the structural unit derived from (meth) acrylic acid or an ester thereof, for example, a structural unit derived from styrene, a structural unit derived from a vinyl compound, or the like may be contained.

From the viewpoint of pattern shape formability, solubility in a developer, and transferability, the resist layer composition preferably contains, as a polymer component, a polymer having a structural unit b1 represented by formula II as the structural unit b, and the resist layer composition preferably contains, as a polymer component, a specific polymer having a structural unit b1 represented by formula II as the structural unit b and having a glass transition temperature of 90 ℃ or less, and the resist layer composition more preferably contains, as a polymer component, a specific polymer having a structural unit b1 represented by formula II as the structural unit b and a structural unit bb having an acid group described later and having a glass transition temperature of 90 ℃ or less.

The number of the specific polymers contained in the resist layer composition may be only 1, or may be 2 or more.

< structural unit b >)

The polymer component contains a polymer having at least a structural unit b containing a group in which an acid group is protected by an acid-decomposable group. The polymer component contains a polymer having a structural unit b, and thus a chemically amplified positive resist layer composition having extremely high sensitivity can be obtained.

The "acid group protected with an acid-decomposable group" in the present invention may use a known group as the acid-decomposable group, and is not particularly limited. As the acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an acetal functional group such as an ester group, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group, which is protected by a group represented by formula II described later) or a group which is relatively hardly decomposed by an acid (for example, a tertiary alkyl carbonate group such as a tertiary butyl ester group or a tertiary alkyl carbonate group such as a tertiary butyl carbonate group) can be used.

Among these, the acid-decomposable group is preferably a group having a structure protected in the form of acetal.

From the viewpoint of sensitivity and resolution, the structural unit b in which the acid group has a group protected with an acid-decomposable group is preferably a structural unit b1 represented by formula II below.

[ chemical formula 8]

In the formula II, R¹And R²Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R¹And R²Any of which is alkyl or aryl, R³Represents alkyl or aryl, R¹Or R²Or with R³Linked to form a cyclic ether, R⁴Represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group.

In the formula II, R¹Or R²When the alkyl group is used, the alkyl group preferably has 1 to 10 carbon atoms. R ¹Or R²In the case of aryl, phenyl is preferred. R¹And R²Preferably hydrogen atom or alkyl group having 1 to 4 carbon atoms.

In the formula II, R³Represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

And, R¹～R³The alkyl group and the aryl group in (1) may have a substituent.

In the formula II, R¹Or R²Or with R³Linked to form a cyclic ether, preferably R¹Or R²And R³Linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, more preferably 5.

In formula II, X represents a single bond or an arylene group, preferably a single bond. The arylene group may have a substituent.

The specific polymer contains the structural unit b1 represented by formula II, and thus the sensitivity at the time of pattern formation is excellent and the resolution is more excellent.

In the formula II, R⁴Represents a hydrogen atom or a methyl groupFrom the viewpoint of further lowering the glass transition temperature (Tg) of the specific polymer, a hydrogen atom is preferable.

More specifically, R in formula II is relative to the total amount of structural unit b1 contained in the specific polymer⁴The structural unit that is a hydrogen atom is preferably 20 mass% or more.

Furthermore, in the structural unit b1, R in the formula II ⁴The content (content ratio: mass ratio) of the structural unit which is a hydrogen atom can be determined by¹³C-nuclear magnetic resonance spectroscopy (NMR) measurement and confirmation were performed according to the intensity ratio of peak intensities calculated by a usual method.

Among the structural units b1 represented by formula II, the structural unit represented by formula b2 is preferable from the viewpoint of further improving the sensitivity in pattern formation.

[ chemical formula 9]

In the formula b2, R³⁴Represents a hydrogen atom or a methyl group, R³⁵～R⁴¹Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula b2, R³⁴Preferably a hydrogen atom.

In the formula b2, R³⁵～R⁴¹Preferably a hydrogen atom.

As a preferable specific example of the structural unit b1 having a group in which an acid group is protected with an acid-decomposable group represented by formula II, the following structural unit can be exemplified. In addition, R³⁴Represents a hydrogen atom or a methyl group.

[ chemical formula 10]

< structural unit b3 >)

In addition, from the viewpoint of suppressing the deformation of the pattern shape, the structural unit b is preferably a structural unit b3 represented by the following formula b 3.

[ chemical formula 11]

In the formula b3, R^B1And R^B2Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R^B1And R^B2Any of which is alkyl or aryl, R^B3Represents alkyl or aryl, R ^B1Or R^B2Can be reacted with R^B3Linked to form a cyclic ether, R^B4Represents a hydrogen atom or a methyl group, X^BRepresents a single bond or a divalent linking group, R^B12Represents a substituent, and n represents an integer of 0 to 4.

In the formula b3, R^B1Or R^B2When the alkyl group is used, the alkyl group preferably has 1 to 10 carbon atoms. R^B1Or R^B2In the case of aryl, phenyl is preferred. R^B1And R^B2Each of which is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula b3, R^B3Represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

And, R^B1～R^B3The alkyl group and the aryl group in (1) may have a substituent.

In the formula b3, R^B1Or R^B2Can be reacted with R^B3Linked to form a cyclic ether, preferably R^B1Or R^B2And R^B3Linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, more preferably 5.

In the formula b3, X^BRepresents a single bond or a divalent linking group, and is preferably a single bond or an alkylene group, -C (═ O) O-, -C (═ O) NR^N-, -O-or a combination of these, more preferably a single bond. The alkylene group may be linear, branched, or have a cyclic structure, and may have a substituent. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 4. X ^Bwhen-C (═ O) O-is contained, it is preferable that the carbon atom contained in-C (═ O) O-is bonded to R^B4The carbon atom of (A) is directly bonded toFormula (II) is shown. X^Bcontaining-C (═ O) NR^NIn the case of-O, it is preferably-C (═ O) NR^NCarbon atom contained in (A) and a bond R^B4The carbon atoms of (b) are directly bonded. RN represents an alkyl group or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and more preferably a hydrogen atom.

In the formula b3, containing R^B1～R^B3Group of (2) and X^BPreferably bonded in para-position to each other.

In the formula b3, R^B12Represents a substituent, preferably an alkyl group or a halogen atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4.

In the formula b3, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the formula b3, R^B4Represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of further lowering the Tg of the specific polymer.

More specifically, R in the formula b3 is represented by the following formula b3 relative to the total content of the structural unit b contained in a specific polymer^B4The structural unit that is a hydrogen atom is preferably 20 mass% or more.

R in the structural unit b and in the formula b3^B4The content (content ratio: mass ratio) of the structural unit which is a hydrogen atom can be determined by¹³C-nuclear magnetic resonance spectroscopy (NMR) measurement and confirmation were performed according to the intensity ratio of peak intensities calculated by a usual method.

Among the structural units represented by the formula b3, the structural unit represented by the following formula b4 is preferable from the viewpoint of suppressing the deformation of the pattern shape.

[ chemical formula 12]

In the formula b4, R^B4Represents a hydrogen atom or a methyl group, R^B5～R^B11Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R^B12Represents a substituent, and n represents an integer of 0 to 4.

In the formula b4, R^B4Preference is given toIs a hydrogen atom.

In the formula b4, R^B5～R^B11Preferably a hydrogen atom.

In the formula b4, R^B12Represents a substituent, preferably an alkyl group or a halogen atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4.

In the formula b4, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

As a preferred specific example of the structural unit b4 represented by the formula b4, the following structural units can be exemplified. In addition, R^B4Represents a hydrogen atom or a methyl group.

[ chemical formula 13]

The number of the structural units b contained in the specific polymer may be 1, or 2 or more.

The content of the structural unit b in the specific polymer is preferably 20% by mass or more, more preferably 20% by mass to 90% by mass, and still more preferably 30% by mass to 70% by mass, based on the total mass of the specific polymer.

The content (content ratio: mass ratio) of the structural unit b in the specific polymer can be determined by ¹³C-NMR measurement and confirmation were carried out by calculating the intensity ratio of peak intensities according to a usual method.

After all the polymer components are decomposed into the structural units (monomer units), the proportion of the structural unit b is preferably 5 to 80% by mass, more preferably 10 to 80% by mass, particularly preferably 10 to 40% by mass, and most preferably 10 to 30% by mass, based on the total mass of the polymer components.

< structural unit bb >

The above-mentioned specific polymer preferably contains a structural unit bb having an acid group.

The structural unit bb is a structural unit containing an acid group which is not protected by a protecting group such as an acid-decomposable group, i.e., an acid group having no protecting group. By including the structural unit bb in the specific polymer, the sensitivity at the time of pattern formation becomes good, and the specific polymer is easily dissolved in an alkaline developer in a developing step after pattern exposure, and the development time can be shortened.

The introduction of the structural unit having an acid group into the specific polymer can be performed by copolymerizing a monomer having an acid group.

The structural unit containing an acid group as the structural unit bb is more preferably a structural unit obtained by substituting an acid group for a structural unit derived from styrene or a structural unit derived from a vinyl compound or a structural unit derived from (meth) acrylic acid.

The number of the structural units bb included in a specific polymer may be 1, or 2 or more.

The specific polymer preferably contains a structural unit having an acid group (structural unit bb) in an amount of 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and still more preferably 1 to 10% by mass, based on the total mass of the specific polymer. When the amount is within the above range, the pattern formability is further improved.

The content (content ratio: mass ratio) of the structural unit b in the specific polymer can be determined by¹³C-NMR measurement and confirmation were carried out by calculating the intensity ratio of peak intensities according to a usual method.

Other structural units

The specific polymer may contain other structural units (hereinafter, sometimes referred to as structural unit bbb.) in addition to the structural unit b and the structural unit bb described above, within a range that does not impair the effects of the photosensitive transfer material according to the present invention.

The monomer forming the structural unit bbb is not particularly limited, and examples thereof include styrenes, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, aryl (meth) acrylates, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic anhydrides, groups having an aliphatic cyclic skeleton, and other unsaturated compounds.

By adjusting at least one of the kind and the content of the structural unit bbb, various properties of a specific polymer can be adjusted. In particular, by appropriately using the structural unit bbb, the Tg of the specific polymer can be easily adjusted to 90 ℃ or lower.

The specific polymer may contain only 1 structural unit bbb, or may contain 2 or more.

Specifically, the structural unit bbb may be a structural unit formed of styrene, t-butoxystyrene, methylstyrene, α -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, or polymerized ethylene glycol monoacetoacetate mono (meth) acrylate. Further, compounds described in paragraphs 0021 to 0024 of Japanese patent laid-open No. 2004-264623 can be mentioned.

In addition, from the viewpoint of improving the electrical characteristics of the obtained photosensitive transfer material, the structural unit bbb is preferably a structural unit having an aromatic ring or a structural unit having an aliphatic ring skeleton. Specific examples of the monomer forming these structural units include styrene, t-butoxystyrene, methylstyrene, α -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate. Among these, preferred as the structural unit bbb is a structural unit derived from cyclohexyl (meth) acrylate.

In addition, the monomer forming the structural unit bbb is preferably, for example, alkyl (meth) acrylate from the viewpoint of adhesiveness. Among these, alkyl (meth) acrylates having an alkyl group having 4 to 12 carbon atoms are 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 bbb is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less, based on the total mass of the specific polymer. The lower limit may be 0 mass%, but is preferably 1 mass% or more, and more preferably 5 mass% or more. When the amount is within the above range, the resolution and the adhesion of the resist layer formed from the resist layer composition are further improved.

From the viewpoint of optimizing the solubility in a developer and the physical properties of a resist layer described later, it is also preferable that the specific polymer contains, as the structural unit bbb, a structural unit of an ester having an acid group in the structural unit bb.

Among them, the specific polymer contains a structural unit having an acid group as a structural unit bb, preferably further contains a structural unit bbb having a carboxylate group as a copolymerization component, and more preferably contains, for example, a structural unit bb derived from (meth) acrylic acid and a structural unit derived from cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate.

Preferred examples of the specific polymer in the present invention will be described below, but the present invention is not limited to the examples below. The ratio of the structural units and the weight-average molecular weight in the following exemplary compounds can be appropriately selected in order to obtain preferable physical properties.

[ chemical formula 14]

< glass transition temperature of specific polymer: tg >)

The glass transition temperature (Tg) of the specific polymer in the present invention is preferably 90 ℃ or lower. The Tg of 90 ℃ or lower allows a resist layer formed from the resist layer composition to have high adhesion and to have excellent transferability.

The Tg is more preferably 60 ℃ or lower, and still more preferably 40 ℃ or lower.

The lower limit of the Tg is not particularly limited, but is preferably-20 ℃ or higher, more preferably-10 ℃ or higher. When the Tg of the specific polymer is-20 ℃ or higher, good pattern formability is maintained, and, for example, when a cover film is used, the decrease in peelability when peeling the cover film is suppressed.

In the present invention, the glass transition temperature (Tg) of the entire polymer component is preferably 90 ℃ or lower, more preferably 60 ℃ or lower, and still more preferably 40 ℃ or lower, from the viewpoint of transferability.

The glass transition temperature of a particular polymer can be measured using a Differential Scanning Calorimeter (DSC).

The specific measurement method was carried out in accordance with the procedure of the method described in JIS K7121 (1987) or JIS K6240 (2011). The glass transition temperature in the present invention is an extrapolated glass-origin temperature (hereinafter, sometimes referred to as Tig).

The method for measuring the glass transition temperature will be described more specifically.

When the glass transition temperature is determined, the device is held at a temperature about 50 ℃ lower than the predicted Tg of the polymer until it is stable, and then the glass transition temperature is determined at a heating rate: 20 ℃/min, to a temperature about 30 ℃ higher than the temperature at which the glass pellet has ended, and plotting a DTA curve or a DSC curve.

The glass transition temperature Tg in the present invention, the external glass transition temperature (Tig), was determined as follows: the temperature of the intersection point of the tangent line drawn by the curve extending the reference line on the low temperature side along the high temperature side and the stepwise change in glass in the DTA curve or DSC curve becomes the maximum point.

As a method for adjusting Tg of the specific polymer to the above-described preferable range, Tg of the target specific polymer can be controlled based on FOX formula, for example, by Tg of a homopolymer of each structural unit of the target polymer and a mass ratio of each structural unit.

With respect to the formula FOX,

when Tg of the homopolymer of the 1 st structural unit contained in the polymer component is Tg1, mass fraction of the copolymer of the 1 st structural unit is W1, Tg of the homopolymer of the 2 nd structural unit is Tg2, and mass fraction of the copolymer of the 2 nd structural unit is W2, Tg0(K) of the copolymer containing the 1 st structural unit and the 2 nd structural unit can be estimated from the following formula.

FOX formula: 1/Tg0 ═ W1/Tg1) + (W2/Tg2)

By using the above formula FOX, a copolymer having a desired Tg can be obtained by adjusting the type and mass fraction of each structural unit contained in the copolymer.

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

< molecular weight of specific polymer: mw >)

The molecular weight of the specific polymer is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight. The weight average molecular weight of the specific polymer is 60,000 or less, whereby the melt viscosity of a resist layer in a photosensitive transfer material described later can be suppressed to a low level, and bonding at a low temperature (for example, 130 ℃ or less) can be achieved when the photosensitive transfer material is bonded to a substrate.

The weight average molecular weight of the specific polymer is preferably 2,000 to 60,000, more preferably 3,000 to 50,000, and still more preferably 10,000 to 30,000.

The weight average molecular weight of the specific polymer can be measured by GPC (gel permeation chromatography), various commercially available devices can be used as the measuring device, and the contents of the devices and the measuring techniques are well known to those skilled in the art.

For the measurement of the weight average molecular weight by Gel Permeation Chromatography (GPC), as a measuring device, HLC (registered trademark) -8220GPC (TOSOH CORPORATION) was used, and as a column, a column in which TSKgel (registered trademark), Super HZM-M (4.6mmID × 15cm, TOSOH CORPORATION), Super HZ4000(4.6mmID × 15cm, TOSOH CORPORATION), Super HZ3000(4.6mmID × 15cm, TOSOH CORPORATION), Super HZ2000(4.6mmID × 15cm, TOSOH CORPORATION), THF (tetrahydrofuran) was used in series was used as an eluent.

The measurement conditions were 0.2 mass% for the sample concentration, 0.35ml/min for the flow rate, 10. mu.l for the sample injection amount, and 40 ℃ for the measurement temperature, and the measurement was performed by a differential Refractive Index (RI) detector.

The calibration curve can be obtained using a "standard TSK standard, polystyrene" manufactured by TOSOH CORPORATION: any of 7 samples of "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500" and "A-1000" was prepared.

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

Production method of specific polymer

The method for producing the specific polymer (synthesis method) is not particularly limited, but examples thereof include the following: the polymerizable monomer for forming the structural unit b1 represented by formula II, the polymerizable monomer for forming the structural unit bb having an acid group, and if necessary, the polymerizable monomer for forming the other structural unit bbb can be synthesized by polymerization using a polymerization initiator. Further, it can be synthesized by a so-called polymer reaction.

From the viewpoint of sensitivity and resolution, the resist layer composition according to the present invention preferably contains the specific polymer at a ratio of 50 to 99.9% by mass, more preferably 70 to 98% by mass, relative to the total solid content of the resist layer composition.

Other polymers

The resist layer composition may contain, as a polymer component, a polymer not containing the structural unit b (which may be referred to as "other polymer") within a range not impairing the effect of the resist layer composition according to the present invention, in addition to the specific polymer.

When the resist layer composition contains another polymer, the amount of the other polymer to be blended is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less, of the total polymer components.

Further, all the polymers contained in the polymer component are preferably polymers each having at least a structural unit containing the acid group.

The plasticizer, the heterocyclic compound, and the compound corresponding to the surfactant, which will be described later, are not included in the polymer component, even if they are polymer compounds.

The resist layer composition may contain only 1 kind of other polymer, or 2 or more kinds of other polymers, in addition to the specific polymer.

As the other polymer, for example, polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA2000P, SMA 3000P, SMA 1440 35 1440F, SMA 17352P, SMA 2625P and SMA 3840F (see above, made by Sartomer company, Inc.), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920 and ARUFON UC-3080 (see above, made by TOAGOSEI CO., LTD.), Joncryl 690, Joncryl 678, Joncryl 67 and Joncryl 586 (see above, made by BASF) and the like can be used.

< photoacid generator [ (component (C) ]

The resist layer composition according to the present invention preferably contains a photoacid generator.

The photoacid generator used in the present invention is a compound that can generate an acid by irradiation with radiation such as ultraviolet light, far ultraviolet light, X-rays, and charged particle beams.

The photoacid generator used in the present invention is a compound that generates an acid by being sensitive to actinic rays having a wavelength of 300nm or more, preferably 300nm to 450nm, but the chemical structure is not limited. Further, even a photoacid generator which is not directly sensitive to actinic rays having a wavelength of 300nm or more can be used in combination with a sensitizer as long as it is a compound which is used together with the sensitizer to generate an acid by being sensitive to actinic rays having a wavelength of 300nm or more.

From the viewpoint of sensitivity and visibility, the pKa of the acid generated by the photoacid generator used in the present invention is preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less. The lower limit of the pKa of the acid generated by the specific photoacid generator is not particularly limited, but is preferably, for example, at least-10.0, more preferably at least-4.0, even more preferably at least-3.5, and particularly preferably at least-3.0, from the viewpoint of sensitivity and visibility.

In view of sensitivity and visibility, the acid generated by the photoacid generator is preferably at least 1 acid selected from the group consisting of phosphoric acids and sulfonic acids, more preferably a sulfonic acid, and even more preferably a sulfonic acid represented by formula C1 or formula C2.

[ chemical formula 15]

In the formulae C1 and C2, R^SRepresents an alkyl group, L^SRepresents an alkylene group having 2 or more carbon atoms, ns represents 0 or 1, wherein R is^SIn the case of an alkyl group having a halogen atom, n is 1, X^SEach independently represents an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and ms represents an integer of 0 to 5.

R^SThe alkyl group in (1) may have a substituent.

Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, and an aryloxy group.

R^SThe number of carbon atoms of the alkyl group in (1) to (20), more preferably (2) to (16).

L^SPreferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and particularly preferably an ethylene group.

X^SEach of the alkyl groups is preferably an alkyl group, more preferably an alkyl group having 1 to 20 carbon atoms, still more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably a methyl group.

ms is preferably an integer of 0 to 3, more preferably 0 or 1, and particularly preferably 1.

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

The photoacid generator preferably contains at least 1 compound selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound described later, and more preferably contains an oxime sulfonate compound, from the viewpoint of sensitivity and resolution.

Examples of the nonionic photoacid generator include trichloromethyl s-triazine compounds, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds, and the like. Among these, the photoacid generator is preferably an oxime sulfonate compound from the viewpoint of sensitivity, resolution, and adhesion. These photoacid generators can be used alone in 1 kind or in combination of 2 or more kinds. Specific examples of trichloromethyl s-triazine and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494.

The oxime sulfonate compound, i.e., a compound having an oxime sulfonate structure, is preferably a compound having an oxime sulfonate structure represented by the following formula C3.

[ chemical formula 16]

In the formula C3, R²¹Represents an alkyl group or an aryl group, and represents a bonding site with another atom or another group.

In the compound having an oxime sulfonate structure represented by the formula C3, all of the groups may be substituted, R ²¹The alkyl group in (2) may be linear, may have a branched structure, or may have a cyclic structure. The following are descriptions of permissible substituents.

As R²¹The alkyl group of (3) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. R²¹The alkyl group (C) may be substituted with an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (including a bridged alicyclic group such as 7, 7-dimethyl-2-oxonorbornyl group, preferably a bicycloalkyl group) or a halogen atom.

As R²¹Aryl of (2), preferably carbon atomAryl groups having a sub-number of 6 to 18 are more preferably phenyl or naphthyl. R²¹The aryl group (C) may be substituted with at least one group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group and a halogen atom.

The compound having an oxime sulfonate structure represented by the formula C3 is preferably an oxime sulfonate compound described in paragraphs 0078 to 0111 of Japanese patent application laid-open No. 2014-085643.

Examples thereof include compounds described in paragraphs 0080 to 0081 of Japanese patent laid-open publication No. 2015-151347.

Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Among these, onium salt compounds are preferred, and triarylsulfonium salts and diaryliodonium salts are particularly preferred.

The ionic photoacid generators described in paragraphs 0114 to 0133 of jp 2014-085643 a can also be suitably used as the ionic photoacid generators.

The photoacid generator may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

From the viewpoint of sensitivity and resolution, the content of the photoacid generator in the resist layer composition is preferably 0.1 to 15 mass%, more preferably 0.5 to 10 mass%, with respect to the total solid content of the resist layer composition.

< polymerizable Compound >

When the photosensitive transfer material in the present invention is a negative photosensitive transfer material, the resist layer composition preferably contains a polymerizable compound.

The polymerizable compound is preferably an ethylenically unsaturated compound.

The ethylenically unsaturated compound is a component contributing to the photosensitivity (i.e., photocurability) of the photosensitive transfer material and the strength of the cured film.

The ethylenically unsaturated compound is a compound having 1 or more ethylenically unsaturated groups.

The resist layer composition preferably contains an ethylenically unsaturated compound having 2 or more functions as the ethylenically unsaturated compound.

The term "ethylenically unsaturated compound having 2 or more functions" as used herein means a compound having 2 or more ethylenically unsaturated groups in one molecule.

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

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

The 2-functional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds.

Examples of the 2-functional ethylenically unsaturated compound include tricyclodecane dimethanol di (meth) acrylate, 1, 9-nonane diol di (meth) acrylate, and 1, 6-hexane diol di (meth) acrylate.

More specifically, the 2-functional ethylenically unsaturated compound includes tricyclodecane dimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Co., manufactured by Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., manufactured by Ltd.), 1, 9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., manufactured by Ltd.), and 1, 6-hexanediol diacrylate (A-HD-N, Shin-Nakamura Chemical Co., manufactured by Ltd.), and the like.

Further, as the 2-functional ethylenically unsaturated compound, a 2-functional ethylenically unsaturated compound having a bisphenol structure is also preferably used.

Examples of the 2-functional ethylenically unsaturated compound having a bisphenol structure include those described in paragraphs 0072 to 0080 of Japanese patent application laid-open No. 2016-224162.

Specifically, alkylene oxide (alkylene oxide) -modified bisphenol a di (meth) acrylate and the like can be mentioned, and 2, 2-bis (4- (methacryloyloxydiethoxy) phenyl) propane, 2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane and the like are preferably used.

The ethylenically unsaturated compound having 3 or more functions is not particularly limited, and can be appropriately selected from known compounds.

Examples of the 3-or more-functional ethylenically unsaturated compound include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, neopentanetetraol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and a (meth) acrylate compound having a glycerol tri (meth) acrylate skeleton.

In the above description, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.

Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth) acrylate compounds (e.g., Nippon Kayaku Co., Ltd., KAYARAD (registered trademark) DPCA-20, Shin-Nakamura Chemical Co., Ltd., A-9300-1 CL., Ltd.), alkylene oxide (alkylene oxide) modified compounds of (meth) acrylate compounds (e.g., Nippon Kayaku Co., Ltd., KAYARAD RP-1040, Shin-Nakamura Chemical Co., Ltd., ATM-35E, A-9300, DAICEL-ALLNEX LTD., EBECRYL (registered trademark) 135, etc.), ethoxylated glycerol triacrylate (e.g., Shin-Nakamura Chemical Co., Ltd., A-GLY-9E, etc.).

The ethylenically unsaturated compound may also be a urethane (meth) acrylate compound (preferably a 3-or more-functional urethane (meth) acrylate compound).

Examples of the 3-or more-functional urethane (meth) acrylate compound include 8UX-015A (TAISEI FINE CHEMICAL Co, manufactured by Ltd.), UA-32P (Shin-Nakamura Chemical Co., manufactured by Ltd.), UA-1100H (Shin-Nakamura Chemical Co., manufactured by Ltd.), and the like.

From the viewpoint of improving developability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group.

Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group is preferable.

Examples of the ethylenically unsaturated compound having an acid group include 3 to 4-functional ethylenically unsaturated compounds having an acid group (a compound having a carboxyl group introduced into a neopentyltetraol tri-and tetraacrylate (PETA) skeleton (acid value: 80mgKOH/g to 120mgKOH/g)), 5 to 6-functional ethylenically unsaturated compounds having an acid group (a compound having a carboxyl group introduced into a dipentaerythritol penta-and hexaacrylate (DPHA) skeleton (acid value: 25mgKOH/g to 70mgKOH/g)), and the like.

If necessary, the 3-or more-functional ethylenically unsaturated compound having these acid groups may be used in combination with the 2-functional ethylenically unsaturated compound having acid groups.

The ethylenically unsaturated compound having an acid group is preferably at least 1 selected from the group consisting of a carboxyl group-containing ethylenically unsaturated compound having 2 or more functions and a carboxylic acid anhydride thereof.

The carboxyl group-containing 2-or more-functional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds.

As the carboxyl group-containing 2-or more-functional ethylenically unsaturated compound, for example, ARONIX (registered trademark) TO-2349(TOAGOSEI CO., LTD., manufactured by LTD.), ARONIX M-520(TOAGOSEI CO., LTD., manufactured by LTD.), or ARONIX M-510(TOAGOSEI CO., LTD., manufactured by LTD.) can be preferably used.

The ethylenically unsaturated compound having an acid group is preferably a polymerizable compound having an acid group as described in paragraphs 0025 to 0030 of Japanese patent application laid-open No. 2004-239942. The content of this publication is incorporated in the present invention.

The polymerizable compound used in the present invention has a weight average molecular weight (Mw) of preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

The content of the polymerizable compound having a molecular weight of 300 or less in the polymerizable compound used in the resist layer composition is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less, based on the total amount of the ethylenically unsaturated compound contained in the resist layer composition.

The polymerizable compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The content of the polymerizable compound in the resist layer composition is preferably 1 to 70% by mass, more preferably 10 to 70% by mass, even more preferably 20 to 60% by mass, and particularly preferably 20 to 50% by mass, based on the total mass of the resist layer composition.

When the resist layer composition contains a 2-functional ethylenically unsaturated compound and a 3-or more-functional ethylenically unsaturated compound, the content of the 2-functional ethylenically unsaturated compound is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and still more preferably 30 to 80% by mass, based on the total amount of the ethylenically unsaturated compounds contained in the resist layer composition.

In these cases, the content of the 3-or more-functional ethylenically unsaturated compound is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and still more preferably 20 to 70% by mass, based on the total ethylenically unsaturated compound contained in the resist layer composition.

In these cases, the content of the 2-or more-functional ethylenically unsaturated compound is preferably 40% by mass or more and less than 100% by mass, more preferably 40% by mass to 90% by mass, even more preferably 50% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass, based on the total content of the 2-or more-functional ethylenically unsaturated compound and the 3-or more-functional ethylenically unsaturated compound.

When the resist layer composition contains an ethylenically unsaturated compound having 2 or more functions, the resist layer composition may further contain a monofunctional ethylenically unsaturated compound.

In the case where the resist layer composition contains an ethylenically unsaturated compound having 2 or more functions, the ethylenically unsaturated compound having 2 or more functions is preferably a main component among the ethylenically unsaturated compounds contained in the resist layer composition.

Specifically, when the resist layer composition contains an ethylenically unsaturated compound having 2 or more functions, the content of the ethylenically unsaturated compound having 2 or more functions is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass, based on the total content of the ethylenically unsaturated compounds contained in the resist layer composition.

When the resist layer composition contains an ethylenically unsaturated compound having an acid group (preferably, an ethylenically unsaturated compound having 2 or more functions of a carboxyl group or a carboxylic acid anhydride thereof), the content of the ethylenically unsaturated compound having an acid group is preferably 1 to 50% by mass, more preferably 1 to 20% by mass, and still more preferably 1 to 10% by mass, based on the resist layer composition.

< adhesive Polymer having acid group >

In the case where the photosensitive transfer material in the present invention is a negative photosensitive transfer material, the resist layer composition preferably contains a binder polymer having an acid group.

As the binder polymer having an acid group, an alkali-soluble resin is preferable.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphate group, and a phosphonic acid group.

Among them, preferable examples of the acid group include a carboxyl group.

The acid value of the binder polymer having the acid group is not particularly limited, but from the viewpoint of alkali developability, an alkali-soluble resin having an acid value of 60mgKOH/g or more is preferable, and a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more is particularly preferable.

The carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more (hereinafter, may be referred to as a specific polymer a.) is not particularly limited as long as the above-mentioned conditions for the acid value are satisfied, and can be appropriately selected from known resins and used.

For example, an alkali-soluble resin, which is a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more, in the polymer described in paragraph 0025 of Japanese patent application laid-open No. 2011-095716, a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more, in the polymer described in paragraphs 0033 to 0052 of Japanese patent application laid-open No. 2010-237589, and a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more, in the binder polymer described in paragraphs 0053 to 0068 of Japanese patent application laid-open No. 2016-224162 can be preferably used as the specific polymer A in the present invention.

The (meth) acrylic resin is a resin containing at least one of a structural unit derived from (meth) acrylic acid and a structural unit derived from a (meth) acrylate ester.

The total ratio of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester in the (meth) acrylic resin is preferably 30 mol% or more, and more preferably 50 mol% or more.

The copolymerization ratio of the monomer having a carboxyl group in the specific polymer a is preferably in the range of 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 12 to 30% by mass, based on 100% by mass of the polymer.

The specific polymer a may have a reactive group, and examples of the mechanism for introducing a reactive group into the specific polymer a include a method of reacting an epoxy compound, a blocked isocyanate, an isocyanate, a vinyl sulfone compound, an aldehyde compound, a methylol compound, a carboxylic anhydride, or the like with a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group, a sulfonic acid, or the like.

The specific polymer a is preferably a compound a shown below. The content ratio of each structural unit shown can be appropriately changed according to the purpose.

[ chemical formula 17]

Compound A

The acid value of the binder polymer having an acid group used in the present invention is preferably 60mgKOH/g to 200mgKOH/g, more preferably 60mgKOH/g to 150mgKOH/g, and still more preferably 60mgKOH/g to 110mgKOH/g, from the viewpoint of alkali developability.

In the present invention, the acid value refers to a value measured according to the method described in JIS K0070 (1992).

The weight average molecular weight of the binder polymer having an acid group is preferably 1,000 or more, more preferably 1 ten thousand or more, and further preferably 2 to 10 ten thousand.

The binder polymer having an acid group can be used by appropriately selecting an arbitrary film-forming resin according to the purpose, in addition to the specific polymer a. For example, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin and the like can be preferably used.

The binder polymer having an acid group may be used alone in 1 kind, or may contain 2 or more kinds.

From the viewpoint of photosensitivity, the content of the binder polymer having an acid group in the resist layer composition is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and still more preferably 30% by mass or more and 70% by mass or less, with respect to the total mass of the resist layer composition.

< photopolymerization initiator >

In the case where the photosensitive transfer material in the present invention is a negative photosensitive transfer material, the resist layer composition preferably contains a photopolymerization initiator. The photopolymerization initiator receives actinic rays such as ultraviolet rays and visible rays to start polymerization of the polymerizable compound (ethylenically unsaturated compound).

The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as an "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α -aminoalkylbenzophenone structure (hereinafter, also referred to as an "α -aminoalkylbenzophenone-based photopolymerization initiator"), a photopolymerization initiator having an α -hydroxyalkylphenone structure (hereinafter, also referred to as an "α -hydroxyalkylphenone-based polymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as an "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter, also referred to as an "N-phenylglycine-based photopolymerization initiator").

The photopolymerization initiator preferably contains at least 1 selected from the group consisting of oxime-based photopolymerization initiators, α -aminoalkylphenyl ketone-based photopolymerization initiators, α -hydroxyalkylphenyl ketone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators, and more preferably contains at least 1 selected from the group consisting of oxime-based photopolymerization initiators, α -aminoalkylphenyl ketone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators.

Further, it is preferable that the photopolymerization initiator further contains at least 1 selected from the group consisting of 2,4, 5-triarylimidazole dimers and derivatives thereof. The 2,4, 5-triarylimidazole dimer and its derivative may be a compound represented by the following formula PI.

[ chemical formula 18]

In the formula PI, X¹And X²At least 1 of them is preferably a chlorine atom. AR¹、AR²、AR³And AR⁴When each of the substituents independently has a substituent, the number of the substituents is preferably 1 to 5, more preferably 1 to 3, and further preferably 1. And, AR¹、AR²、AR³And AR⁴When each of the substituents independently has a substituent, the substitution position is not particularly limited, and is preferably an ortho-position or a para-position. p and q are each independently an integer of preferably 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1.

Examples of the compound represented by the formula PI include 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, and 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer. In addition, 2,4, 5-three aryl imidazole aryl substituents can be assigned to the same and symmetrical compounds, also can be assigned to different and asymmetric compounds.

Further, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of Japanese patent application laid-open No. 2011-095716 and paragraphs 0064 to 0081 of Japanese patent application laid-open No. 2015-014783 may be used.

Commercially available photopolymerization initiators include 1- [4- (phenylthio) ] -1, 2-octanedione-2- (o-benzoyloxime) (product name: IRGACURE (registered trademark) OXE-01, manufactured by BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (o-acetyloxime) (product name: IRGACURE OXE-02, manufactured by BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone (product name: IRGACURE 379EG, manufactured by BASF corporation), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- Ketone (product name: IRGACURE 907, manufactured by BASF Corp.), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one (product name: IRGACURE 127, manufactured by BASF Corp.), 2-benzyl-2-dimethylamino-1- (4-morpholino) butanone-1 (product name: IRGACURE 369, manufactured by BASF Corp.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (product name: IRGACURE 1173, manufactured by BASF Corp.), 1-hydroxycyclohexyl phenyl ketone (product name: IRGACURE 184, manufactured by BASF Corp.), 2-dimethoxy-1, 2-diphenylethan-1-one (product name: IRGACURE 651, BASF corporation), oxime ester type photopolymerization initiator (product name: lunar 6, manufactured by DKSH JAPAN k.k.), 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenylbisimidazole (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer) (product name: B-CIM, manufactured by Hampford corporation), and the like.

The photopolymerization initiator may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The content of the photopolymerization initiator in the resist layer composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more, relative to the total mass of the resist layer composition.

The content of the photopolymerization initiator is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the resist layer composition.

Polymerization inhibitors

When the photosensitive transfer material according to the present invention is a negative photosensitive transfer material, the resist layer composition may contain at least 1 polymerization inhibitor.

As the polymerization inhibitor, for example, the thermal polymerization inhibitor described in paragraph 0018 of japanese patent No. 4502784 can be used.

Among them, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.

When the resist layer composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 3% by mass, more preferably 0.01 to 1% by mass, and still more preferably 0.01 to 0.8% by mass, based on the total mass of the resist layer composition.

< basic Compound [ (component (D) ]

The resist layer composition according to the present invention preferably contains a basic compound.

The basic compound can be arbitrarily selected from among basic compounds used for chemically amplified resists. 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 Japanese patent application laid-open No. 2011-221494, and the contents thereof are incorporated in the present invention.

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

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

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

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

Examples of the quaternary ammonium salt of a carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate, and the like.

The above basic compounds can be used alone in 1 kind, also can be combined with more than 2 kinds.

The content of the basic compound is preferably 0.001 to 5% by mass, and more preferably 0.005 to 3% by mass, based on the total solid content of the resist layer composition.

< solvent >

The resist layer composition according to the present invention preferably further contains a solvent (S).

In order to facilitate formation of a resist layer described later, the resist layer composition may be preferably formed by temporarily containing a solvent to adjust the viscosity of the resist layer composition, and applying and drying the resist layer composition containing the solvent.

As the solvent used in the present invention, a known solvent can be used. Examples of the solvent include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides and lactones, 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, and the like. Specific examples of the solvent include those described in paragraphs 0174 to 0178 of Japanese patent application laid-open No. 2011-221494, and these are incorporated in the present invention.

Further, if necessary, a solvent such as benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, or propylene carbonate may be added to the above-described solvent.

The solvent may be used in 1 kind or 2 or more kinds.

The solvent which can be used in the present invention may be used alone in 1 kind, and more preferably in 2 kinds in combination. When 2 or more solvents are used, for example, a combination of propylene glycol monoalkyl ether acetates and dialkyl ethers, a combination of diacetates and diethylene glycol dialkyl ethers, or a combination of esters and butanediol alkyl ether acetates is preferable.

The solvent is preferably a solvent having a boiling point of 130 ℃ or higher and less than 160 ℃, a solvent having a boiling point of 160 ℃ or higher, or a mixture of these solvents.

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

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

The content of the solvent in applying the resist layer composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the resist layer composition.

The content of the solvent in the resist layer described later is preferably 2% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less, based on the total mass of the resist layer.

< other additives >

The resist layer composition of the present invention may contain known additives as needed, in addition to the above components such as the specific polymer and the photoacid generator.

Plasticizer-

The resist layer composition of the present invention may contain a plasticizer for the purpose of improving plasticity.

The weight average molecular weight of the plasticizer is preferably less than the weight average molecular weight of the specific polymer.

From the viewpoint of imparting plasticity, the weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, and further preferably 800 or more and less than 4,000.

The plasticizer is not particularly limited as long as it is a compound that is compatible with the specific polymer and exhibits plasticity, but from the viewpoint of imparting plasticity, it is preferable that the plasticizer has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.

[ chemical formula 19]

In the formula, R is alkylene with 2-8 carbon atoms, n represents an integer of 1-50, and x represents a bonding part with other atoms.

For example, even in the case of a compound having an alkyleneoxy group of the above-described structure (referred to as "compound X"), the plasticizer in the present invention is not satisfied when the plasticity of a chemically amplified positive resist layer composition obtained by mixing the compound X, the specific polymer, and the photoacid generator is not improved as compared with a chemically amplified positive resist layer composition formed without including the compound X. For example, an arbitrarily added surfactant is not generally used in an amount that imparts plasticity to the resist layer composition, and therefore does not meet the plasticizer in the present invention.

The content of the plasticizer is preferably 1 to 50% by mass, and more preferably 2 to 20% by mass, based on the total solid content of the resist layer composition, from the viewpoint of adhesion of the resist layer formed from the resist layer composition.

The resist layer composition may contain only 1 kind of plasticizer, or may contain 2 or more kinds.

Sensitizers-

The resist layer composition according to the present invention can further contain a sensitizer.

The sensitizer absorbs actinic rays to become an electron excited state. The sensitizer in the electron excited state is brought into contact with the photoacid generator to generate an action of electron movement, energy movement, heat generation, and the like. This causes the photoacid generator to chemically change, thereby decomposing and generating an acid.

By containing a sensitizer, exposure sensitivity can be improved.

As the sensitizer, a compound selected from the group consisting of anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, basic styrene derivatives and stilbene styrene derivatives is preferable, and anthracene derivatives are more preferable.

As the anthracene derivative, preferred is anthracene, 9, 10-dibutoxyanthracene, 9, 10-dichloroanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9, 10-dibromoanthracene, 2-ethylanthracene or 9, 10-dimethoxyanthracene.

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

The content of the sensitizer is preferably 0 to 10% by mass, more preferably 0.1 to 10% by mass, based on the total solid content of the resist layer composition.

Heterocyclic compounds

The resist layer composition according to the present invention can contain a heterocyclic compound.

The heterocyclic compound in the present invention is not particularly limited. For example, a compound having an epoxy group or an oxetanyl group in the molecule, a heterocyclic compound containing an alkoxymethyl group, other various cyclic ethers, an oxygen-containing monomer such as a cyclic ester (lactone), a nitrogen-containing monomer such as a cyclic amine or oxazoline, a heterocyclic monomer having d-electrons such as silicon, sulfur or phosphorus, and the like, which are described below, can be added.

When a heterocyclic compound is added, the content of the heterocyclic compound in the resist layer composition is preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass, and still more preferably 1 to 5% by mass, based on the total solid content of the resist layer composition. In the above range, the composition is preferable from the viewpoint of adhesion and etching resistance. The heterocyclic compounds may be used in a single amount of 1 kind, or in combination of 2 or more kinds.

Specific examples of the compound having an epoxy group in the molecule include bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like.

A compound having an epoxy group in the molecule can be obtained as a commercially available product. Examples thereof include JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation), and commercial products described in paragraph 0189 of Japanese patent application laid-open publication No. 2011-221494.

Other commercially available products include ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKARESIN EP-4010S, ADEKA RESIN EP-4011S (manufactured by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA CORPORATION), DENACOL EX-611, EX-612, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX-121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192 (manufactured by Nagase Chemtex Corporation, supra), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD.) CELLOXIDE 2021P, 2081, 2000, 3000, EHPE EPON 3150, LEAD GT400, SERUBINASU B0134, B0177 (manufactured by Daicel Corporation), and the like.

The compound having an epoxy group in the molecule may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Among the compounds having an epoxy group in the molecule, bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, and aliphatic epoxy resins are more preferable, and aliphatic epoxy resins are particularly preferable.

Specific examples of the compound having an oxetanyl group in the molecule include Aron Oxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ and PNOX (TOAGOSEI CO., LTD., supra).

The oxetanyl group-containing compound is preferably used alone or in a mixture with an epoxy group-containing compound.

In the resist layer composition according to the present invention, a compound in which the heterocyclic compound has an epoxy group is preferable from the viewpoint of the etching resistance and the line width stability of the obtained pattern.

An alkoxysilane compound

The resist layer composition according to the present invention may contain an alkoxysilane compound. As the alkoxysilane compound, a trialkoxysilane compound is preferably cited.

Examples of the alkoxysilane compound include γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, γ -glycidoxypropyltrialkoxysilane, γ -glycidoxypropylalkyldialkoxysilane, γ -methacryloxypropyltrialkoxysilane, γ -methacryloxypropylalkyldialkoxysilane, γ -chloropropyltrialkoxysilane, γ -mercaptopropyltrialkoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrialkoxysilane, and vinyltrialkoxysilane. Of these, gamma-glycidoxypropyltrialkoxysilane or gamma-methacryloxypropyltrialkoxysilane is more preferable, gamma-glycidoxypropyltrialkoxysilane is further preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. These can be used alone 1 or a combination of 2 or more.

The content of the alkoxysilane compound is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, based on the total solid content of the resist layer composition.

Surfactants-

The resist layer composition according to the present invention preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, Nonionic (Nonionic) and amphoteric surfactants can be used, but a preferred surfactant is a Nonionic surfactant.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. Further, the following product names include KP (Shin-Etsu Chemical Co., manufactured by Ltd.), POLYFLOW (Kyoeisha Chemical Co., manufactured by Ltd.), EFTOP (manufactured by JEMCO CORPORATION), MEGAFACE (DIC CORPORATION Co., manufactured by Ltd.), FLUORAD (manufactured by Sumitomo 3M Limited), ASAHI GUARD, SURFLON (ASAHI GLASS CO., manufactured by LTD.), PolyFox (manufactured by OMNOVA SOLUTION INC.), SH-8400 (manufactured by Dow Corning Toray Co., Ltd.), and the like.

The surfactant contains a structural unit a and a structural unit B represented by the following formula I-1, and a preferable example thereof is a copolymer having a weight average molecular weight (Mw) of 1,000 to 10,000 in terms of polystyrene as measured by gel permeation chromatography using Tetrahydrofuran (THF) as a solvent.

[ chemical formula 20]

In the formula (I-1), R⁴⁰¹And R⁴⁰³Each independently represents a hydrogen atom or a methyl group, R⁴⁰²Represents a linear alkylene group having 1 to 4 carbon atoms, R⁴⁰⁴Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are percentages by mass indicating a polymerization ratio, p represents a numerical value of 10 to 80 mass%, q represents a numerical value of 20 to 90 mass%, r represents an integer of 1 to 18, s represents an integer of 1 to 10, and x represents a bonding site with another structure.

L is preferably a branched alkylene group represented by the following formula (I-2). R in the formula (I-2)⁴⁰⁵The alkyl group having 1 to 4 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 2 or 3 carbon atoms, from the viewpoint of compatibility and wettability with respect to the surface to be coated. The sum of p and q (p + q) is preferably 100, i.e., 100 mass%.

[ chemical formula 21]

The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.

The surfactants described in paragraphs 0017 of Japanese patent No. 4502784 and 0060 to 0071 of Japanese patent application laid-open No. 2009-237362 can also be used.

The surfactant may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The amount of the surfactant added is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and still more preferably 0.01% by mass to 3% by mass, based on the total solid content of the resist layer composition.

Other ingredients-

The resist layer composition of the present invention may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid proliferators, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, tackifiers, and organic or inorganic deposition inhibitors.

Preferred embodiments of the other components are described in paragraphs 0165 to 0184 of Japanese patent application laid-open No. 2014-085643, the contents of which are incorporated in the present invention.

The resist layer may preferably contain components of the resist layer composition other than the solvent.

In the resist layer, the preferable content of each component with respect to the total mass of the resist layer is the same as the preferable content of each component with respect to the total solid content of the resist layer composition in the resist layer composition.

Thickness of the resist layer

The thickness of the resist layer is preferably 0.5 to 20 μm. If the thickness of the resist layer is 20 μm or less, the resolution of the obtained pattern is good, and if it is 0.5 μm or more, it is preferable from the viewpoint of pattern linearity.

The thickness of the resist layer is more preferably 0.8 to 15 μm, and particularly preferably 1.0 to 10 μm.

Method for forming resist layer

The resist layer-forming composition for forming a resist layer can be prepared by mixing and dissolving the respective components and the solvent at predetermined ratios by an arbitrary method with stirring. For example, the compositions can be prepared by dissolving the respective components in a solvent in advance, and then mixing the resulting solutions at a predetermined ratio. The composition prepared as above can also be used after being filtered with a filter having a pore size of 0.2 μm or the like.

The photosensitive transfer material of the present invention having the intermediate layer and the resist layer on the temporary support can be obtained by applying the resist layer composition onto the temporary support having the intermediate layer formed thereon and drying the composition. The coating method is not particularly limited, and coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.

[ temporary support ]

The photosensitive transfer material according to the present invention has a temporary support.

The temporary support supports the intermediate layer and the resist layer and is a support that can be peeled off.

The temporary support used in the present invention is preferably light-transmissive, from the viewpoint that the intermediate layer and the resist layer can be exposed via the temporary support when the intermediate layer and the resist layer are pattern-exposed.

Having light transmittance means that the transmittance of the dominant wavelength of light used for pattern exposure is 50% or more, and from the viewpoint of improving exposure sensitivity, the transmittance of the dominant wavelength of light used for pattern exposure is preferably 60% or more, and more preferably 70% or more. As a method for measuring the transmittance, a method of measuring by MCPD Series manufactured by Otsuka Electronics co.

Examples of the temporary support include a glass substrate, a resin film, and paper, and the resin film is particularly preferable from the viewpoint of strength, flexibility, and the like. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of the temporary support is not particularly limited, but is preferably in the range of 5 μm to 200 μm, and more preferably in the range of 10 μm to 150 μm from the viewpoints of ease of handling, versatility, and the like.

The thickness of the temporary support may be selected according to the material, from the viewpoints of the strength of the support, the flexibility required for bonding to the circuit wiring forming substrate, the light transmittance required in the first exposure step, and the like.

A preferred embodiment of the temporary support is described in, for example, paragraphs 0017 to 0018 of japanese patent application laid-open No. 2014-085643, the contents of which are incorporated in the present invention.

[ other layers ]

The photosensitive transfer material according to the present invention may have a layer (hereinafter, sometimes referred to as "other layer") other than the intermediate layer and the resist layer. Examples of the other layers include a contrast reinforcing layer, a cover film, and a thermoplastic resin layer.

The photosensitive transfer material of the present invention includes an intermediate layer and a resist layer in this order on a temporary support.

Here, referring to fig. 1 and 2, an example of the layer structure of the photosensitive transfer material according to the present invention is schematically shown.

The photosensitive transfer material 100 shown in fig. 1 is formed by laminating a temporary support 12, a laminate 14 (see fig. 2) of a resist layer 14-1 and an intermediate layer 14-2, and a cover film 16 in this order. The intermediate layer 14-2 contains a pigment.

The following describes constituent materials of the photosensitive transfer material according to the present invention. The above-described configuration of the present invention is sometimes referred to as follows in the present invention.

A polymer having a structural unit containing a group in which an acid group is protected with an acid-decomposable group is sometimes referred to as a "specific polymer".

When the resist layer is a positive resist layer, it is sometimes referred to as a "positive resist layer". When the resist layer is a negative resist layer, the resist layer may be referred to as a "negative resist layer".

(method of manufacturing Circuit Wiring)

Embodiment 1 of a method for manufacturing a circuit wiring using the photosensitive transfer material according to the present invention will be described.

Embodiment 1 of the method for manufacturing a circuit wiring includes the steps of:

a step (bonding step) of bonding the photosensitive transfer material according to the present invention to a substrate so that the resist layer of the photosensitive transfer material is in contact with the substrate;

a step (exposure step) of pattern-exposing the intermediate layer and the resist layer of the photosensitive transfer material after the step of bonding;

a step (developing step) of forming a pattern by developing the resist layer after the pattern exposure step; and a step (etching step) of etching the substrate in the region where no pattern is disposed.

The substrate in embodiment 1 of the method for manufacturing a circuit wiring may be a substrate in which a desired layer such as a conductive layer is provided on a base material such as glass, silicon, or a thin film.

According to embodiment 1 of the method for manufacturing a circuit wiring, a fine pattern can be formed on the surface of a substrate.

Embodiment 2 of the method for manufacturing a circuit wiring includes the steps of:

a bonding step of bonding a substrate having a base and a plurality of conductive layers including a 1 st conductive layer and a 2 nd conductive layer which are different from each other in constituent material, in which the resist layer of the photosensitive transfer material according to the present invention is brought into contact with the 1 st conductive layer, in order of separating from the surface of the base, with respect to a substrate on which the 1 st conductive layer and the 2 nd conductive layer are laminated, which is an outermost layer;

a 1 st exposure step of pattern-exposing the intermediate layer and the resist layer via the temporary support of the photosensitive transfer material after the bonding step;

a 1 st developing step of forming a 1 st pattern by removing the temporary support from the intermediate layer and the resist layer after the 1 st exposure step and then developing the intermediate layer and the resist layer after the 1 st exposure step;

A 1 st etching step of etching at least the 1 st conductive layer and the 2 nd conductive layer in the plurality of conductive layers in a region where the 1 st pattern is not arranged;

a 2 nd exposure step of pattern-exposing the 1 st pattern after the 1 st etching step with a pattern different from the 1 st pattern;

a 2 nd developing step of forming a 2 nd pattern by developing the 1 st pattern after the 2 nd exposure step; and

and a 2 nd etching step of etching at least the 1 st conductive layer among the plurality of conductive layers in a region where the 2 nd pattern is not arranged. As embodiment 2, international publication No. 2006/190405 can be referred to, and the contents thereof are incorporated in the present invention.

Embodiment 3 of the method of manufacturing a circuit wiring is a method of repeating embodiment 1 2 times.

Namely, the method sequentially comprises:

a step (bonding step) of bonding the resist layer of the photosensitive transfer material according to the present invention to a substrate so as to be in contact with the substrate;

A step (developing step) of forming a pattern by developing the resist layer after the pattern exposure step; and

the step (etching step) of performing etching treatment on the substrate in the region where no pattern is disposed further includes, in order:

a step (bonding step) of bonding the resist layer of the photosensitive transfer material according to the present invention to the remaining resist layer after the etching step, in contact with the remaining resist layer;

and a step (etching step) of performing etching treatment on the substrate in the region where no pattern is disposed.

The photosensitive transfer materials for the 1 st and 2 nd passes may be the same or different. The photosensitive transfer material used in the 1 st laminating step is preferably a positive type, and the photosensitive transfer material used in the 2 nd laminating step may be either a positive type or a negative type.

Embodiment 3 of the method for manufacturing a circuit wiring can be specifically implemented by the following method, for example.

A substrate for forming a conductive pattern was prepared by forming ITO on a base material by sputtering and forming copper thereon by a vacuum evaporation method.

Next, a photosensitive transfer material is bonded to the copper layer to form a laminate. The laminate is pattern-exposed using a mask having a pattern A for connecting the conductive layer pads in one direction without peeling the temporary support. After that, the temporary support is peeled off, and development and water washing are performed to obtain a resin pattern drawn with the pattern a. Next, after the copper layer was etched using a copper etching solution, the ITO layer was etched using an ITO etching solution, thereby obtaining a substrate in which copper was drawn together with ITO using the pattern a.

Next, a photosensitive transfer material is bonded to the remaining resist layer. In this state, pattern exposure is performed using a mask having an opening portion of the pattern B in an aligned state, and after the temporary support of the photosensitive transfer material is peeled, development and washing are performed. Thereafter, the copper wiring is etched and stripped off using the remaining resist layer, thereby obtaining a circuit wiring substrate having a conductive pattern.

The method for manufacturing a circuit wiring according to the present invention can be used as a method for manufacturing a circuit wiring for a touch panel or a touch panel display device.

Hereinafter, details of each step will be described with reference to embodiment 2.

< bonding Process >

Fig. 2(a) schematically shows an example of the bonding step.

First, in the bonding step, a plurality of conductive layers including a base 22 and a 1 st conductive layer 24 and a 2 nd conductive layer 26 which are different in constituent material from each other are provided, and the resist layer 14-1 (see fig. 1) of the photosensitive transfer material 100 according to the present invention described above is bonded to the 1 st conductive layer 24 in contact with the substrate (circuit wiring forming substrate) 20 in which the 1 st conductive layer 24 and the 2 nd conductive layer 26 are laminated as the outermost layer in the order of being separated from the surface of the base 22. The bonding of these circuit wiring forming substrates to a photosensitive transfer material is sometimes referred to as "transfer" or "lamination".

As shown in fig. 1 to 2, when the cover film 16 is provided on the positive resist layer 14 of the photosensitive transfer material 100, the cover film 16 is removed from the photosensitive transfer material 100 (positive resist layer 14), and then the resist layer 14-1 of the photosensitive transfer material 100 is brought into contact with the 1 st conductive layer 24 and bonded thereto.

The adhesion (transfer) of the photosensitive transfer material to the 1 st conductive layer is preferably performed by superposing the resist layer side of the photosensitive transfer material on the 1 st conductive layer and applying pressure and heat by a roller or the like. In the bonding, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator capable of improving productivity can be used.

When the substrate of the circuit wiring forming substrate is a resin film, roll-to-roll bonding can be performed.

[ base Material ]

In the substrate in which a plurality of conductive layers are stacked on a base material, the base material is preferably a glass base material or a film base material, and more preferably a film base material. When the method for manufacturing a circuit wiring according to the present invention is a circuit wiring for a touch panel, the base material is preferably a sheet-like resin composition.

Also, the substrate is preferably transparent. Transparent means that the transmittance in the visible light region, i.e., 400nm to 800nm, is 90% or more.

The refractive index of the base material is preferably 1.50 to 1.52.

The substrate may be composed of a light-transmitting substrate such as a glass substrate, and a strengthened glass represented by GORILLA glass produced by Corning Incorporated can be used. As the transparent substrate, materials used in japanese patent application laid-open nos. 2010-086684, 2010-152809, and 2010-257492 can be preferably used.

When a film substrate is used as the substrate, a substrate having no optical strain and a substrate having high transparency are more preferably used, and specific examples of the raw material include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

[ conductive layer ]

As the plurality of conductive layers formed on the substrate, any conductive layer used for a general circuit wiring or a touch panel wiring can be given.

Examples of the material of the conductive layer include a metal and a metal oxide.

Examples of the metal Oxide include ITO (Indium Tin Oxide), IZO (Indium zinc Oxide), and SiO (silicon Oxide)₂And the like. Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, and Mo.

In the method for manufacturing a circuit wiring according to the present invention, it is preferable that at least one of the plurality of conductive layers contains a metal oxide.

The conductive layer is preferably a wiring corresponding to an electrode pattern or an edge extraction portion of a sensor used in a visual recognition portion of the capacitive touch panel.

[ substrate for Forming Circuit Wiring ]

The substrate is a substrate having a conductive layer on a surface of a base material. The conductive layer is patterned to form a circuit wiring. In this example, it is preferable that a plurality of conductive layers of metal oxide, metal, or the like are provided on a film base material such as PET.

< Exposure Process (1 st Exposure Process) >

The exposure step is performed in embodiment 1, and the exposure step 1 is performed in embodiment 2. Fig. 2(b) schematically shows an example of the exposure step (1 st exposure step).

In the exposure step (1 st exposure step), the positive resist layer 14 is pattern-exposed through the temporary support 12 of the photosensitive transfer material after the bonding step.

As examples of the exposure step, the development step, and other steps in the present invention, the methods described in paragraphs 0035 to 0051 of jp 2006-023696 can also be preferably used in the present invention.

For example, a method in which a mask 30 having a predetermined pattern is disposed above the photosensitive transfer material 100 disposed on the 1 st conductive layer 24 (on the side opposite to the side in contact with the 1 st conductive layer 24), and then exposure is performed with ultraviolet light from above the mask through the mask 30, and the like can be given.

The detailed arrangement and specific dimensions of the patterns in the present invention are not particularly limited. From the viewpoint of improving the display quality of a display device (for example, a touch panel) provided with an input device having circuit wiring manufactured by the method for manufacturing circuit wiring according to the present invention and occupying the area of the extraction wiring as small as possible, at least a part of the pattern (particularly, an electrode pattern of the touch panel and a part of the extraction wiring) is preferably a thin line of 100 μm or less, and more preferably 70 μm or less.

The light source used for the exposure can be appropriately selected and used if it can irradiate light (for example, 365nm, 405nm or the like) in a wavelength region where the portion of the photosensitive transfer material to be exposed can be dissolved in the developer. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and the like can be given.

The exposure amount is preferably 5mJ/cm²～200mJ/cm²About, more preferably 10mJ/cm²～100mJ/cm²Left and right.

Further, it is preferable to perform heat treatment before development in order to improve the rectangularity and linearity of the pattern after exposure. The roughness of the pattern edge based on standing waves generated in the resist layer at the time of Exposure can be reduced by a process called Post Exposure Bake (PEB).

The pattern exposure may be performed after the temporary support is peeled from the intermediate layer and the resist layer, or may be performed through the temporary support before the temporary support is peeled, and then the temporary support is peeled. In order to prevent contamination of the mask due to contact between the intermediate layer and the mask or to avoid influence on exposure by foreign substances adhering to the mask, it is preferable to perform exposure without peeling off the temporary support. The pattern exposure may be exposure through a mask or digital exposure using a laser or the like.

< developing step (1 st developing step) >)

The developing step is performed in embodiment 1, and the developing step 1 is performed in embodiment 2. Fig. 2 c schematically shows an example of the developing step (1 st developing step).

In the developing step (1 st developing step), after the temporary support 12 is peeled off from the positive resist layer 14 after the exposure step (1 st exposure step), the positive resist layer 14 after the exposure step (1 st exposure step) is developed to form the 1 st pattern 14A.

The developing step (1 st developing step) is a step of forming a pattern (1 st pattern) by developing the positive resist layer subjected to pattern exposure.

The development of the pattern-exposed positive resist layer can be performed using a developer.

The developing solution is not particularly limited as long as it can remove the exposed portion of the positive resist layer, and a known developing solution such as the developing solution described in japanese patent application laid-open No. 5-072724 can be used.

Specific examples thereof include an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium carbonate solution, an aqueous potassium carbonate solution and an aqueous tetramethylammonium hydroxide solution.

The developer is preferably a developer in which an exposed portion of the positive resist layer is subjected to a dissolution-type developing operation. For example, the developer is preferably an aqueous alkaline developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05mol/L (liter) to 5 mol/L. The developer may further contain an organic solvent having miscibility with water, a surfactant, and the like. As a developer that can be preferably used in the present invention, for example, a developer described in paragraph 0194 of international publication No. 2015/093271 can be mentioned.

The developing method is not particularly limited, and any of spin-on immersion development, shower and spin development, immersion development, and the like can be used. Note that, when the shower development is described, the exposed portion can be removed by blowing a developer into the exposed positive resist layer by shower. After development, a cleaning agent or the like is blown by showering, and preferably, the development residue is removed while being wiped off by a brush or the like. The liquid temperature of the developing solution is preferably 20 to 40 ℃.

Further, a baking step may be provided after the pattern including the resist layer obtained by development is subjected to a heat treatment.

The post-baking is preferably heated in an environment of 8.1kPa to 121.6kPa, and more preferably in an environment of 506.6kPa or higher. On the other hand, it is more preferably carried out under an environment of 1114.6kPa or less, and particularly preferably carried out under an environment of 101.3kPa or less.

The post-baking temperature is preferably from 80 ℃ to 250 ℃, more preferably from 110 ℃ to 170 ℃, and particularly preferably from 130 ℃ to 150 ℃.

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.

The post-baking may be performed in an air atmosphere or in a nitrogen-substituted atmosphere.

The method of manufacturing the circuit wiring according to the present invention may have other steps such as a post-exposure step.

< etching step (1 st etching step) >)

The etching step is performed in embodiment 1, and the etching step 1 is performed in embodiment 2. Fig. 2(d) schematically shows an example of the etching step (1 st etching step).

In the etching step (1 st etching step), at least the 1 st conductive layer 24 and the 2 nd conductive layer 26 among the plurality of conductive layers in the region where the 1 st pattern 14A is not arranged are etched. By etching, the 1 st conductive layer 24A and the 2 nd conductive layer 26A having the same pattern are formed.

The conductive layer can be etched by a known method such as a method described in, for example, paragraphs 0048 to 0054 of jp 2010-152155 a or a method based on dry etching such as known plasma etching.

For example, as a method of etching, a wet etching method in which the substrate is immersed in an etching solution is generally performed. The etching solution used for wet etching may be an acidic type or an alkaline type, as appropriate, depending on the object to be etched.

Examples of the acidic etching solution include an aqueous solution of a single acidic component such as hydrochloric acid, sulfuric acid, hydrofluoric acid, or phosphoric acid, and a mixed aqueous solution of an acidic component and a salt such as ferric chloride, ammonium fluoride, or potassium permanganate. The acidic component may be a component in which a plurality of acidic components are combined.

Examples of the alkaline type etching solution include an aqueous solution of a single alkaline component such as a salt of an organic amine such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine, or tetramethylammonium hydroxide, and a mixed aqueous solution of an alkaline component and a salt such as potassium permanganate. The alkaline component may be a combination of a plurality of alkaline components.

The temperature of the etching solution is not particularly limited, but is preferably 45 ℃ or lower. The 1 st pattern used as an etching mask (etching pattern) in the present invention preferably exhibits particularly excellent resistance to an acidic and alkaline etching solution in a temperature range of 45 ℃ or less. Therefore, the positive resist layer is prevented from being peeled off in the etching step, and a portion where the positive resist layer is not present is also selectively etched.

After the etching step, a cleaning step and a drying step may be performed as necessary in order to prevent contamination of the production line. The cleaning step is performed by cleaning the substrate with pure water at room temperature for 10 to 300 seconds, for example, and the drying step is performed by blowing air with a blowing pressure (0.1 kg/cm) appropriately adjusted²～5kg/cm²Left and right) to be dried.

< 2 nd Exposure Process >

In embodiment 2, the 2 nd exposure step is performed. Fig. 2(e) schematically shows an example of the 2 nd exposure step.

After the 1 st etching step, the 1 st pattern 14A after the 1 st etching step is pattern-exposed in a pattern different from the 1 st pattern.

In the 2 nd exposure step, a 1 st pattern remaining on the 1 st conductive layer is exposed to light at least at a portion of the 1 st conductive layer to be removed in the 2 nd development step, which will be described later.

The same method as the pattern exposure in the 1 st exposure step can be applied except that the pattern exposure in the 2 nd exposure step uses the mask 40 having a different pattern from the mask 30 used in the 1 st exposure step.

< 2 nd developing step >

In embodiment 2 described above, the 2 nd developing step is performed. Fig. 2(f) schematically shows an example of the 2 nd developing step.

In the 2 nd developing step, the 1 st pattern 14A after the 2 nd exposure step is developed to form a 2 nd pattern 14B.

By the development, the 1 st pattern is removed from the portion exposed in the 2 nd exposure step.

In the 2 nd developing step, the same method as that used in the 1 st developing step can be applied.

< 2 nd etching Process >

In embodiment 2, the 2 nd exposure step is performed. Fig. 2(g) schematically shows an example of the 2 nd etching step.

In the second etching step, at least the 1 st conductive layer 24B among the plurality of conductive layers in the region where the 2 nd pattern 14B is not arranged is etched.

The same method as that used in the etching step 1 can be used except that the etching in the etching step 2 is performed by selecting an etching solution corresponding to the conductive layer to be removed by etching.

In the second etching step, it is preferable that the conductive layer is selectively etched less than in the first etching step in accordance with a desired pattern. For example, as shown in fig. 2, the 1 st conductive layer can be formed into a pattern different from the pattern of the 2 nd conductive layer by etching with an etching solution that selectively etches only the 1 st conductive layer 24B in a region where no positive resist layer is disposed.

After the 2 nd etching step is completed, a circuit wiring including the conductive layer 24B and the conductive layer 26A having at least 2 patterns is formed.

< Positive resist layer removing Process >

Fig. 2(h) schematically shows an example of the positive resist layer removing step.

After the 2 nd etching process is completed, the 2 nd pattern 14B remains on a part of the 1 st conductive layer 24B. If the positive resist layer is not necessary, all of the remaining positive resist layer 14B may be removed.

The method of removing the residual positive resist layer is not particularly limited, but a method of removing by means of medicine processing can be mentioned.

As a method for removing the positive resist layer, for example, a method of immersing a substrate having a positive resist layer or the like in a stripping solution which is stirred at preferably 30 to 80 ℃, more preferably 50 to 80 ℃ for 1 to 30 minutes is exemplified.

Examples of the stripping solution include solutions of inorganic basic components such as sodium hydroxide and potassium hydroxide, or organic basic components such as primary amine, secondary amine, tertiary amine and quaternary ammonium salt in water, dimethyl sulfoxide, N-methylpyrrolidone or a mixed solution thereof. The peeling may be performed by a spraying method, a spin coating and immersing method, or the like using a peeling liquid.

The method of manufacturing a circuit wiring according to the present invention may include other arbitrary steps. For example, the following steps are included, but the present invention is not limited to these steps.

< Process for bonding protective film >

In embodiment 2, a step of attaching a light-transmitting protective film (not shown) to the 1 st pattern may be provided after the 1 st etching step and before the 2 nd exposure step.

In this case, it is preferable that the pattern exposure for the 1 st pattern is performed through a protective film in the 2 nd exposure step, and after the 2 nd exposure step, the protective film is peeled off from the 1 st pattern, and then the 2 nd development step is performed.

< Process for reducing reflectance of visible ray >

The method for manufacturing a circuit wiring according to the present invention may include a step of performing a treatment for reducing the reflectance of a part or all of the visible light rays of the plurality of conductive layers on the base material.

Examples of the treatment for reducing the visible light reflectance include oxidation treatment. For example, the visible light reflectance can be reduced by oxidizing copper to form copper oxide and blackening the copper.

Preferable embodiments of the treatment for reducing the visible light reflectance are described in paragraphs 0017 to 0025 of jp 2014-150118 a and paragraphs 0041, 0042, 0048 and 0058 of jp 2013-206315 a, and the contents of these publications are incorporated in the present invention.

< Process for Forming New conductive layer on insulating film >

The method for manufacturing a circuit wiring of the present invention preferably further includes a step of forming an insulating film on the formed circuit wiring and a step of forming a new conductive layer on the insulating film.

With these configurations, the second electrode pattern can be formed while being insulated from the first electrode pattern.

The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be mentioned. Further, an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive material.

The step of forming a new conductive layer on the insulating film is not particularly limited. A new conductive layer having a desired pattern can be formed by photolithography using a photosensitive material having conductivity.

Further, although the description of fig. 2 has been made with reference to the case where circuit wiring having two different patterns is formed on the circuit wiring forming substrate having 2 conductive layers, the number of conductive layers of the substrate to which the circuit wiring manufacturing method according to the present invention is applied is not limited to 2, and the circuit wiring forming substrate on which 3 or more conductive layers are stacked can be used to form circuit wiring patterns having 3 or more conductive layers different from each other by performing the combination of the exposure step, the development step, and the etching step described above 3 times or more.

Although not shown in fig. 2, in the method for manufacturing a circuit wiring according to the present invention, it is also preferable that the base has a plurality of conductive layers on both surfaces thereof, and that a circuit is formed in the conductive layers formed on both surfaces of the base sequentially or simultaneously. With these configurations, a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface and a second conductive pattern is formed on the other surface of the base material can be formed. Further, it is also preferable that the circuit wiring for a touch panel having these structures be formed from both surfaces of the base material in a roll-to-roll manner.

(Circuit Wiring and Circuit Board)

The circuit wiring according to the present invention is a circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention.

The circuit board according to the present invention is a circuit board having a circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention.

The application of the circuit board according to the present invention is not limited, but for example, a circuit board for a touch panel is preferable.

(input device and display device)

An input device is an example of a device including a circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention.

The input device in the present invention is preferably an electrostatic capacitance type touch panel.

The display device of the present invention preferably includes the input device of the present invention.

The display device of the present invention is preferably an image display device such as an organic EL display device or a liquid crystal display device.

(touch Panel and touch Panel display device and method for manufacturing the same)

The touch panel according to the present invention is a touch panel including at least a circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention. The touch panel according to the present invention preferably includes at least a transparent substrate, an electrode, and an insulating layer or a protective layer.

The touch panel display device according to the present invention is a touch panel display device including at least the circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention, and is preferably a touch panel display device including the touch panel according to the present invention.

The method for manufacturing a touch panel or a touch panel display device according to the present invention preferably includes the method for manufacturing a circuit wiring according to the present invention.

The method for manufacturing a touch panel or a touch panel display device according to the present invention preferably includes, in order, a step of bringing the resist layer of the photosensitive transfer material obtained by the method for manufacturing a photosensitive transfer material into contact with the substrate and bonding the resist layer, a step of pattern-exposing the resist layer of the photosensitive transfer material after the step of bonding, a step of developing the resist layer after the step of pattern-exposing to form a pattern, and a step of etching the substrate in a region where the pattern is not arranged. The details of each step are the same as those of each step in the above-described method for manufacturing a circuit wiring, and preferred embodiments are the same.

The touch panel according to the present invention and the detection method in the touch panel display device according to the present invention may be any of known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the electrostatic capacitance system is preferable.

Examples of the Touch panel type include a so-called inline type (for example, described in fig. 5, 6, 7, and 8 of japanese patent laid-open No. 2012-517051), a so-called external-embedded type (for example, described in fig. 19 of japanese patent laid-open No. 2013-168125, and described in fig. 1 and 5 of japanese patent laid-open No. 2012-089102), an OGS (One Glass Solution) type, a TOL (Touch-on-Lens) type (for example, described in fig. 2 of japanese patent laid-open No. 2013-054727), other structures (for example, described in fig. 6 of japanese patent laid-open No. 2013-164871), and various external-hung types (so-called GG, G1 · G2, GFF, GF2, GF1, G1F, and the like).

As the touch panel according to the present invention and the touch panel display device according to the present invention, configurations disclosed in "latest touch panel technology" (published by ltd. on 7/6 th 2009), gorge-tassel-second supervision, "technology and development of touch panel", CMC publication (2004, 12), FPD International 2009Forum T-11 lecture textbook, and Cypress Semiconductor Corporation application note AN2292, etc. can be applied.

Next, embodiment 2 of the photosensitive transfer material according to the present invention will be described.

In the following detailed description of the invention, the term "photosensitive transfer material" is simply used to mean "embodiment 2 of photosensitive transfer material" unless otherwise specified.

(photosensitive transfer Material embodiment 2)

In embodiment 2 of the photosensitive transfer material according to the present invention, the temporary support, the intermediate layer, and the photosensitive resin layer are provided in this order, the intermediate layer contains a water-soluble resin, particles, and a polar compound having at least 1 polar group selected from the group consisting of an acidic group, a basic group, an anionic group, and a cationic group, and an alkyl group having 6 or more carbon atoms, the photosensitive resin layer contains a polymer containing a structural unit having an acid group protected by an acid-decomposable group, and the photosensitive resin layer is in contact with the intermediate layer.

The problem to be solved by embodiment 2 of the photosensitive transfer material according to the present invention is to provide a photosensitive transfer material having excellent adhesion between a photosensitive resin layer and an intermediate layer.

Further, an object of embodiment 2 of the photosensitive transfer material according to the present invention is to provide a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel using the photosensitive transfer material.

In embodiment 2 of the photosensitive transfer material according to the present invention, a photosensitive transfer material having excellent adhesion between the photosensitive resin layer and the intermediate layer can be provided.

Further, according to embodiment 2 of the photosensitive transfer material according to the present invention, a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel using the photosensitive transfer material can be provided.

The photosensitive transfer material according to the present invention is a positive photosensitive transfer material having a positive photosensitive resin layer containing a polymer containing a structural unit having an acid group protected by an acid-decomposable group as described above. The photosensitive resin layer is preferably a chemically amplified positive photosensitive resin layer.

In the case where a conventional photosensitive transfer material is provided so that a photosensitive resin layer is in contact with an intermediate layer, the present inventors have found that the adhesion between the photosensitive resin layer and the intermediate layer is insufficient.

As a result of intensive studies, the present inventors have found that a photosensitive transfer material having the above-described structure can provide a photosensitive transfer material having excellent adhesion between the photosensitive resin layer and the intermediate layer.

Although the detailed expression mechanism of the above-described effects is not clear, it is presumed that the intermediate layer contains a water-soluble resin, particles, and a polar compound having at least 1 polar group selected from the group consisting of an acidic group, a basic group, an anionic group, and a cationic group, and an alkyl group having 6 or more carbon atoms, whereby in the intermediate layer, the polar group is adsorbed to the particle surface, and the alkyl group having 6 or more carbon atoms penetrates into the photosensitive resin layer or interacts with the photosensitive resin layer in a hydrophobic manner (hydrophobic effect), whereby the photosensitive resin layer and the intermediate layer are firmly adhered to each other, and thus the adhesion between the photosensitive resin layer and the intermediate layer is excellent.

The photosensitive transfer material according to embodiment 2 of the present invention will be described in detail below.

< intermediate layer >

The photosensitive transfer material according to the present invention has an intermediate layer in contact with the photosensitive resin layer, and the intermediate layer contains a water-soluble resin, particles, and a polar compound having at least 1 polar group selected from the group consisting of an acidic group, a basic group, an anionic group, and a cationic group, and an alkyl group having 6 or more carbon atoms.

[ polar Compound ]

The intermediate layer contains a polar compound having at least 1 polar group selected from the group consisting of an acidic group, a basic group, an anionic group and a cationic group, and an alkyl group having 6 or more carbon atoms.

The alkyl group having 6 or more carbon atoms in the polar compound may be linear, branched or cyclic, but is preferably a linear alkyl group or a branched alkyl group, and more preferably a linear alkyl group, from the viewpoint of liquid stability in the adhesion between the photosensitive resin layer and the intermediate layer.

The alkyl group having 6 or more carbon atoms in the polar compound is preferably an alkyl group having 6 to 30 carbon atoms, more preferably an alkyl group having 8 to 22 carbon atoms, and particularly preferably an alkyl group having 10 to 16 carbon atoms, from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer.

The polar group is preferably at least 1 structure selected from the group consisting of primary to tertiary amino groups, primary to quaternary ammonium bases, pyridyl groups, pyridinium groups, carboxylic acid groups (carboxyl groups), sulfonic acid groups (sulfo groups), phosphonic acid groups, phosphoric acid groups, carboxylic acid bases, sulfonic acid bases, phosphonic acid bases, phosphoric acid bases, and betaine structures, more preferably at least 1 structure selected from the group consisting of primary to tertiary amino groups, primary to quaternary ammonium bases, pyridyl groups, pyridinium groups, carboxylic acid groups, sulfonic acid groups, carboxylic acid bases, sulfonic acid bases, and betaine structures, further preferably at least 1 structure selected from the group consisting of primary to tertiary amino groups, primary to quaternary ammonium bases, and betaine structures, and particularly preferably primary to tertiary amino groups or primary to quaternary ammonium bases, and most preferably quaternary ammonium bases, from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer.

Among the primary to tertiary amino groups, a tertiary amino group is preferable from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer.

In addition, of the primary to quaternary ammonium bases, a quaternary ammonium base is preferable from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer.

The betaine structure preferably includes a betaine structure having a carboxylate structure and an ammonium structure or a betaine structure having a sulfonate structure and an ammonium structure, and more preferably includes a betaine structure having a sulfonate structure and an ammonium structure.

The polar compound may form other compounds and salts in the intermediate layer. Specifically, for example, when silica particles having a silanol group as an anionic group on the surface and an amine compound are used, an amino group in the amine compound partially reacts with the silanol group to form a salt.

In the above cases, it is presumed that the amine compound contained in the intermediate layer generates both a compound having an amino group and a compound having an ammonium base. As described above, the polar compound may be a compound having a basic group, or a compound having a basic group and a compound having a cationic group may be both generated.

Therefore, in the present invention, the polar group is defined as at least 1 kind of polar group selected from the group consisting of an acidic group, a basic group, an anionic group, and a cationic group.

The polar compound may have only 1 polar group or 2 or more, but from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer and liquid stability in the composition for forming the intermediate layer, a compound having only 1 polar group is preferable. In addition, regarding the betaine structure, the total number of cationic sites and anionic sites is 1.

The counter anion in the above primary to quaternary ammonium bases or the above pyridinium group is not particularly limited, but preferably contains a monovalent anion, more preferably contains a halide ion or a hydroxide ion, and particularly preferably contains a chloride ion or a hydroxide ion.

The counter cation in the carboxylic acid base, the sulfonic acid base, the phosphonic acid base, or the phosphonic acid base is not particularly limited, but preferably includes a monovalent cation, and more preferably includes an alkali metal ion or a primary to quaternary ammonium ion.

The polar compound may be an aliphatic compound or an aromatic compound, but is preferably an aliphatic compound from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer and liquid stability in the composition for forming the intermediate layer.

The molecular weight of the polar compound is not particularly limited, but is preferably 100 to 800, more preferably 120 to 600, and particularly preferably 150 to 400, from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer and liquid stability in the composition for forming the intermediate layer.

Specific examples of the polar compound include primary to tertiary amino compounds, primary to quaternary ammonium salt compounds, carboxylic acid compounds, sulfonic acid compounds, carboxylic acid chloride compounds, sulfonic acid chloride compounds, and the like.

Specific examples of the polar compound include, but are not limited to, the following compounds.

[ chemical formula 22]

[ chemical formula 23]

[ chemical formula 24]

The intermediate layer may contain 1 kind of the above polar compound alone, or 2 or more kinds.

The content of the polar compound in the intermediate layer is preferably 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, even more preferably 0.1 to 1.0% by mass, and particularly preferably 0.2 to 0.8% by mass, based on the total mass of the intermediate layer, from the viewpoints of the adhesion between the photosensitive resin layer and the intermediate layer and the liquid stability in the composition for forming the intermediate layer.

[ particles ]

The intermediate layer contains particles.

The particles are preferably metal oxide particles or organic particles, and more preferably oxide particles or organic particles of an element selected from the group consisting of Si, Ti, and Zr, from the viewpoint of adhesion between the intermediate layer and the photosensitive layer.

The metal of the metal oxide particles in the present invention also includes semimetals such As B, Si, Ge, As, Sb and Te.

The metal oxide particles are preferably oxide particles containing atoms such as Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, Te, etc., more preferably silica, acidified titanium, titanium composite oxide, zinc oxide, zirconium oxide, indium/tin oxide, or antimony/tin oxide, further preferably silica, acidified titanium, titanium composite oxide, or zirconium oxide, particularly preferably silica, acidified titanium, or zirconium oxide, and most preferably silica.

As the organic particles, organic resin particles are preferably mentioned.

Examples of the organic resin particles include homopolymers and copolymers of acrylic monomers such as acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, cellulose polymers such as nitrocellulose, methylcellulose, ethylcellulose, and cellulose acetate, polyethylene, polypropylene, polystyrene, vinyl chloride copolymers, vinyl chloride-vinyl acetate copolymers, vinyl polymers such as polyvinylpyrrolidone, polyvinyl butyral, and polyvinyl alcohol, and copolymers of vinyl compounds, condensation polymers such as polyester, polyurethane, and polyamide, rubber thermoplastic polymers such as butadiene-styrene copolymers, polymers such as photopolymerizable or thermopolymerizable compounds obtained by polymerizing and crosslinking epoxy compounds, and melamine compounds.

Among these, the organic particles are preferably acrylic resin particles, and more preferably polymethyl methacrylate particles.

Among them, from the viewpoint of the adhesion between the intermediate layer and the photosensitive layer, the particles are preferably silica particles.

In addition, in order to impart dispersion stability, the surface of these particles can be treated with an organic material or an inorganic material. The surface of the particles is preferably hydrophilic particles. For example, hydrophilization treatment is performed on the surfaces of particles having hydrophobic surfaces.

In view of the adhesion between the photosensitive resin layer and the intermediate layer and the liquid stability in the composition for forming the intermediate layer, the particles are preferably particles having an anionic group or a cationic group on the surface, more preferably particles having an anionic group on the surface, and particularly preferably silica particles having an anionic group on the surface.

In addition, the polar compound is preferably a polar compound having a basic group or a cationic group, from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer when the intermediate layer is a particle having an anionic group on the surface. In addition, the polar compound is preferably a polar compound having an acidic group or an anionic group, from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer in the case of particles having a cationic group on the surface.

The anionic group on the surface of the particle is preferably a silanol group or a carboxyl group, and more preferably a silanol group.

The cationic group on the surface of the particle is preferably an amino group.

From the viewpoint of adhesion between the intermediate layer and the photosensitive layer, the arithmetic mean particle diameter of the particles is preferably 100nm or less, more preferably 50nm or less, still more preferably 6nm to 30nm, and particularly preferably 1nm to 25 nm.

As for the method of measuring the arithmetic mean particle diameter of the particles in the present invention, 200 particle diameters of arbitrary particles are measured by an electron microscope and referred to as the arithmetic mean thereof. When the shape of the particle is not spherical, the maximum diameter is set to the diameter.

The intermediate layer may contain 1 kind of the particles alone or 2 or more kinds.

The content of the particles in the intermediate layer is preferably 1 to 90 mass%, more preferably 3 to 70 mass%, and particularly preferably 5 to 50 mass% with respect to the total mass of the intermediate layer, from the viewpoint of adhesion between the intermediate layer and the photosensitive layer.

[ Water-soluble resin ]

The intermediate layer contains a water-soluble resin.

In the present invention, "water-soluble" means that the solubility in 100g of water having a pH of 7.0 at 22 ℃ is 0.1g or more.

The water-soluble resin preferably has a solubility in 100g of water having a pH of 7.0 at 22 ℃ of 1g or more, more preferably 5g or more.

Examples of the water-soluble resin include cellulose resins, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, acrylamide resins, (meth) acrylate resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. Among these, cellulose resins are preferable, and at least 1 resin selected from the group consisting of hydroxypropyl cellulose and hydroxypropyl methyl cellulose is more preferable.

The intermediate layer may contain 1 kind of water-soluble resin alone or 2 or more kinds.

From the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer, the content of the water-soluble resin is preferably 10 to 99 mass%, more preferably 30 to 97 mass%, and particularly preferably 50 to 95 mass% with respect to the total mass of the intermediate layer.

[ pH sensitive pigment ]

From the viewpoint of ease of confirmation of an exposure pattern, the intermediate layer preferably contains a pH sensitive dye which has a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm during color development and changes the maximum absorption wavelength by pH.

The "change in maximum absorption wavelength" may be any of a method in which a dye in a colored state is decolored, a method in which a dye in a decolored state is colored, and a method in which a dye in a colored state is changed to a colored state of another color.

From the viewpoint of visibility, the pH-sensitive pigment is more preferably a latent pigment decolored by an acid generated from a photoacid generator.

The confirmation of the pH sensitive pigment can be performed by the following method.

100mL of a mixed solution of 0.1g of a dye dissolved in ethanol and water (ethanol/water: 1/2[ mass ratio ]) was added to a 0.1mol/L (1N) aqueous hydrochloric acid solution to adjust the pH to 1. Titration was carried out with 0.01mol/L (0.01N) aqueous sodium hydroxide solution, and a color development change and a pH at which the color development change appears were confirmed. The pH was measured at 25 ℃ using a pH meter (model: HM-31, manufactured by DKK-TOA CORPORATION).

As for the method of measuring the maximum absorption wavelength in the present invention, a spectrophotometer is used at 25 ℃ in an atmospheric atmosphere: UV3100 (manufactured by Shimadzu Corporation), a transmission spectrum was measured in a range of 400nm to 780nm, and the intensity of light was measured to be an extremely small wavelength (maximum absorption wavelength).

Examples of the dye that is decolorized by exposure include a leuco compound, a diphenylmethane dye, an oxazine dye, a xanthene dye, an iminonaphthoquinone dye, an azomethine dye, and an anthraquinone dye.

Among them, from the viewpoint of visibility, a colorless compound is preferable as the coloring matter.

Examples of the colorless compound include colorless compounds such as triarylmethane-based (e.g., triphenylmethane-based), spiropyran-based, fluorescein-based, diphenylmethane-based, rhodamine-based, indolylphthalein-based, and leuco aureoxide-based compounds. Among them, a colorless compound having a triarylmethane skeleton (triarylmethane-based coloring matter) is preferable, and a triphenylmethane-based coloring matter is more preferable.

From the viewpoint of visibility, the colorless compound is preferably a colorless compound having a lactone ring, a sultone ring, or a sultone ring and having the lactone ring, the sultone ring, or the sultone ring opened or closed, and more preferably a colorless compound having a sultone ring and having the sultone ring closed and decolored.

The dye is preferably a water-soluble compound for the purpose of preventing defects due to precipitation of the dye.

The solubility of the dye in 100g of water having a pH of 7.0 at 22 ℃ is preferably 1g or more, more preferably 5g or more.

The intermediate layer may contain 1 kind of pigment alone or 2 or more kinds of pigments.

The content of the pigment in the intermediate layer is preferably 0.01 to 10% by mass, more preferably 0.5 to 5% by mass, and still more preferably 1.0 to 3.0% by mass, based on the total mass of the intermediate layer, from the viewpoint of visibility.

[ surfactant ]

The intermediate layer preferably contains a surfactant from the viewpoint of thickness uniformity. As the surfactant, any of a surfactant having a fluorine atom, a surfactant having a silicon atom, and a surfactant having neither a fluorine atom nor a silicon atom can be used. Among them, from the viewpoint of suppressing the generation of texture and adhesion in the photosensitive resin layer and the intermediate layer, the surfactant is preferably a surfactant having a fluorine atom, and more preferably a surfactant having a perfluoroalkyl group and a polyalkyleneoxy group.

As the surfactant, any of anionic, cationic, nonionic (nonionic) and amphoteric surfactants can be used, but a nonionic surfactant is preferable.

From the viewpoint of suppressing precipitation of the surfactant, the surfactant preferably has a solubility of 1g or more with respect to 100g of water at 25 ℃.

The intermediate layer may contain 1 kind of surfactant alone or 2 or more kinds.

The content of the surfactant in the intermediate layer is preferably 0.05 to 2.0% by mass, more preferably 0.1 to 1.0% by mass, and particularly preferably 0.2 to 0.5% by mass, based on the total mass of the intermediate layer, from the viewpoint of suppressing the occurrence of texture and adhesion in the photosensitive resin layer and the intermediate layer.

[ pH adjusting agent ]

The intermediate layer can include a pH adjuster. By including the pH adjuster, the colored state or decolored state of the pigment in the intermediate layer can be maintained more stably, and the adhesion between the photosensitive resin layer and the intermediate layer can be further improved.

The pH adjuster in the present invention is not particularly limited. Examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, organic amines, organic ammonium salts and the like. From the viewpoint of water solubility, sodium hydroxide is preferred. From the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer, an organic ammonium salt is preferable.

As the pH adjuster, an acidic pH adjuster may be used. Examples thereof include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid and toluenesulfonic acid. From the viewpoint of substrate stability, an organic acid is preferable.

< average thickness of intermediate layer >)

The average thickness of the intermediate layer is preferably 0.3 to 10 μm, more preferably 0.3 to 5 μm, and particularly preferably 0.3 to 3 μm, from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer and pattern formability.

The average thickness of the intermediate layer is preferably smaller than the average thickness of the photosensitive resin layer.

Method for forming interlayer

The intermediate layer in the present invention can be formed by preparing an intermediate layer-forming composition containing the components used for forming the intermediate layer and a water-soluble solvent, and coating and drying the composition. After the components are dissolved in the solvent in advance, the resulting solutions may be mixed at a predetermined ratio to prepare a composition. The composition prepared as described above can also be prepared by using a filter having a pore size of 3.0. mu.m.

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 coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.

[ composition for Forming intermediate layer ]

The intermediate layer-forming composition preferably contains a component used for forming the intermediate layer and a water-soluble solvent. The intermediate layer can be preferably formed by adjusting the viscosity by adding a water-soluble solvent to each component, and applying and drying the mixture.

Water-soluble solvent-

The water-soluble solvent may be a known water-soluble solvent, and preferably includes water, alcohols having 1 to 6 carbon atoms, and the like. Specific examples of the alcohol having 1 to 6 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, and n-hexanol. Among them, at least 1 selected from the group consisting of methanol, ethanol, n-propanol and isopropanol is preferably used.

< Water-soluble resin layer >

The photosensitive transfer material of the present invention further has a water-soluble resin layer having a particle content of preferably 5 mass% or less between the temporary support and the intermediate layer, from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer and adhesion between the temporary support and the intermediate layer.

The water-soluble resin layer may contain a water-soluble resin and the content of the particles is 5% by mass or less, or may contain no particles when the content of the particles is 0% by mass.

In view of storage stability and adhesion between the photosensitive resin layer and the intermediate layer, the water-soluble resin layer preferably contains a smaller amount of particles than the intermediate layer.

The water-soluble resin layer preferably contains the polar compound, and when the intermediate layer is applied in multiple layers on the upper layer of the water-soluble resin layer and dried or in a subsequent step, the polar compound in the water-soluble resin layer is diffused into the intermediate layer to form the intermediate layer containing the polar compound and the particles.

The water-soluble resin layer contains a water-soluble resin.

The water-soluble resin used in the water-soluble resin layer may be the same as the water-soluble resin used in the intermediate layer, and preferred embodiments are also the same.

The water-soluble resin layer may contain 1 kind of water-soluble resin alone, or may contain 2 or more kinds.

From the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer, the content of the water-soluble resin is preferably 50 to 100 mass%, more preferably 65 to 99 mass%, and particularly preferably 80 to 98 mass% with respect to the total mass of the water-soluble resin layer.

The water-soluble resin layer may contain particles when the content thereof is 5% by mass or less.

The particles used in the water-soluble resin layer may be the same as those used in the intermediate layer, and preferred embodiments are also the same.

The water-soluble resin layer may contain 1 kind of particles alone, or 2 or more kinds.

From the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer, the content of the particles is preferably 3 mass% or less, and more preferably 1 mass% or less, with respect to the total mass of the water-soluble resin layer.

The water-soluble resin layer may also contain a polar compound.

The polar compound used in the water-soluble resin layer may be the same as the polar compound used in the intermediate layer, and the preferred embodiment is the same.

The water-soluble resin layer may contain 1 kind of polar compound alone, or may contain 2 or more kinds.

From the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer and liquid stability in the composition for forming the intermediate layer, the content of the polar compound is preferably 0.01 to 5 mass%, more preferably 0.05 to 2 mass%, even more preferably 0.1 to 1.0 mass%, and particularly preferably 0.2 to 0.8 mass% with respect to the total mass of the water-soluble resin layer.

The water-soluble resin layer may contain other compounds than the above.

The other compound used in the water-soluble resin layer is not particularly limited, and the same compound as that used in the intermediate layer can be used, and preferred embodiments are also the same.

The average thickness of the water-soluble resin layer is preferably 0.3 to 10 μm, more preferably 0.3 to 5 μm, and particularly preferably 0.3 to 2.5 μm, from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer and pattern formability.

In view of adhesion between the intermediate layer and the photosensitive resin layer and pattern formability, the average thickness of the water-soluble resin layer is preferably larger than the average thickness of the intermediate layer.

Method for forming water-soluble resin layer

The method for forming the water-soluble resin layer is not particularly limited, and a known method can be used.

In the case of forming a water-soluble resin layer, a sequential coating method or a multilayer coating method can be preferably used as a method for forming the water-soluble resin layer and the intermediate layer.

Even in the case of formation by the sequential coating method, since the binder component of the water-soluble resin layer and the intermediate layer is a water-soluble resin, the water-soluble resin layer-forming composition is applied to the temporary support and dried to form the water-soluble resin layer, and when the intermediate layer-forming composition is applied to the formed water-soluble resin layer, the water-soluble resin layer is partially dissolved and mixed with the intermediate layer-forming composition, and for example, part of the particles in the intermediate layer-forming composition moves to the water-soluble resin layer, and part of the polar compound contained in the water-soluble resin layer moves to the intermediate layer, which is the intermediate layer-forming composition.

Even when a water-soluble resin layer-forming composition not containing particles is used, the water-soluble resin layer may be a layer containing particles, and even when a particle-containing layer-forming composition not containing the polar compound is used, the particle-containing layer may be a layer containing the polar compound.

In the case where the water-soluble resin layer and the intermediate layer are formed by a multilayer coating method, the mixing is considered to be more remarkable.

The water-soluble resin layer-forming composition used for forming the water-soluble resin layer may or may not contain particles, but preferably does not contain particles from the viewpoint of liquid stability of the water-soluble resin layer-forming composition.

In addition, from the viewpoint of the liquid stability of the water-soluble resin layer-forming composition, it is preferable that the water-soluble resin layer-forming composition used for forming the water-soluble resin layer contains a polar compound.

In the case of using a water-soluble resin layer-forming composition containing a polar compound, the intermediate layer-forming composition used for forming the intermediate layer may or may not contain the polar compound, but preferably does not contain the polar compound from the viewpoint of liquid stability of the intermediate layer-forming composition.

The water-soluble resin layer-forming composition can be prepared in the same manner as the above-described intermediate layer-forming composition except that the content of the particles is small. The water-soluble resin layer can be preferably formed by adding a water-soluble solvent to each component to adjust the viscosity and applying and drying the mixture.

< photosensitive resin layer >

The photosensitive transfer material according to the present invention has a photosensitive resin layer.

The photosensitive resin layer in the present invention is a positive photosensitive resin layer. From the viewpoint of sensitivity and resolution, the photosensitive resin layer used in the present invention is preferably a chemically amplified positive photosensitive resin layer containing an acid-decomposable resin, i.e., a polymer having a structural unit containing an acid group protected by an acid-decomposable group, and a photoacid generator.

Since an acid generated by the reaction of a photoacid generator such as an onium salt or an oxime sulfonate compound described later with active radiation (actinic ray) acts as a catalyst for deprotection of a protected acid group in the polymer, the acid generated by the action of 1 photon contributes to a large number of deprotection reactions, and the quantum yield exceeds 1 and becomes a value as large as, for example, a power of 10, and as a result of so-called chemical amplification, high sensitivity can be obtained.

On the other hand, when a quinone di-compound is used as a photoacid generator which is sensitive to actinic rays, a carboxyl group is generated by a sequential photochemical reaction, but the quantum yield thereof must be 1 or less, and a chemically amplified type is not satisfied.

[ Polymer X having structural Unit A containing acid group protected with acid-decomposable group ]

The photosensitive resin layer is preferably a polymer X (simply referred to as "polymer X") containing a structural unit a (simply referred to as "structural unit a") containing an acid group protected with an acid-decomposable group.

The photosensitive resin layer may contain other polymers in addition to the polymer X having the structural unit a. In the present invention, the polymer X having the structural unit a and other polymers are collectively referred to as "polymer components".

The polymer X is subjected to deprotection reaction of an acid group protected by an acid-decomposable group in the polymer X by the action of an acidic substance such as a catalyst amount of acid generated by exposure to light, and becomes an acid group. The acid group can dissolve the photosensitive resin layer in a developer.

The polymer X is preferably an addition polymerization type resin, and more preferably a polymer having a structural unit derived from (meth) acrylic acid or an ester thereof. In addition, the resin composition may have a structural unit other than a structural unit derived from (meth) acrylic acid or an ester thereof, for example, a structural unit derived from a styrene compound, a structural unit derived from a vinyl compound, or the like.

Preferred embodiments of the structural unit a are described below.

Structural unit A-

The polymer component is preferably a polymer X containing a structural unit a having an acid group protected with an acid-decomposable group. By including the polymer X having the structural unit a in the photosensitive resin layer, a chemically amplified positive photosensitive resin layer with extremely high sensitivity can be prepared.

The acid group and the acid-decomposable group in the present invention are not particularly limited, and known acid groups and acid-decomposable groups can be used. Specific examples of the acid group include a carboxyl group and a phenolic hydroxyl group. Examples of the acid-decomposable group include groups which are relatively easily decomposed by an acid (for example, acetal-type protecting groups such as 1-alkoxyalkyl group, tetrahydropyranyl group, and tetrahydrofuranyl group) and groups which are relatively easily decomposed by an acid (for example, tertiary alkyl groups such as t-butyl group, and tertiary alkyl oxycarbonyl groups (carbonate-type protecting groups) such as t-butyloxycarbonyl group).

In addition, from the viewpoint of suppressing a change in line width of the conductive wiring when applied to the formation of a conductive pattern, the acid-decomposable group preferably has a molecular weight of 300 or less.

The number of the polymers X contained in the photosensitive resin layer may be only 1, or may be 2 or more.

From the viewpoint of sensitivity and resolution, the structural unit a having an acid group protected with an acid-decomposable group is preferably a structural unit represented by formula a1, formula a2, or formula A3.

[ chemical formula 25]

In the formula A1, R¹¹And R¹²Each independently represents a hydrogen atom, an alkyl group or an aryl group, R¹¹And R¹²At least one of which is alkyl or aryl, R¹³Represents alkyl or aryl, R¹¹Or R¹²And R¹³May be linked to form a cyclic ether, R¹⁴Represents a hydrogen atom or a methyl group, X¹Represents a single bond or a divalent linking group, R¹⁵Represents a substituent, and n represents an integer of 0 to 4.

In the formula A2, R²¹And R²²Each independently represents a hydrogen atom, an alkyl group or an aryl group, R²¹And R²²At least one of which is alkyl or aryl, R²³Represents alkyl or aryl, R²¹Or R²²And R²³May be linked to form a cyclic ether, R²⁴Each independently represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.

In the formula A3, R³¹And R³²Each independently represents a hydrogen atom, an alkyl group or an aryl group, R³¹And R ³²At least one of which is alkyl or aryl, R³³Represents alkyl or aryl, R³¹Or R³²Can be reacted with R³³Linked to form a cyclic ether, R³⁴Represents a hydrogen atom or a methyl group, X⁰Represents a single bond or a divalent linking group.

In the formula A3, R³¹Or R³²In the case of an alkyl group, the number of carbon atoms is preferably 1 to 10. R³¹Or R³²In the case of aryl, phenyl is preferred. R³¹And R³²Each of which is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula A3, R³³Represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

And, R³¹～R³³The alkyl group and the aryl group in (1) may have a substituent.

In the formula A3, R³¹Or R³²Can be reacted with R³³Linked to form a cyclic ether, preferably R³¹Or R³²And R³³Linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, more preferably 5.

In the formula A3, X⁰Represents a single bond or an arylene group, preferably a single bond. The arylene group may have a substituent.

The structural unit a represented by the formula a3 is a structural unit having a carboxyl group protected with an acetal type acid-decomposable group. When the polymer X contains the structural unit a represented by the formula a3, the sensitivity at the time of pattern formation is excellent and the resolution is further excellent.

In the formula A3, R³⁴Represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of further lowering the glass transition temperature (Tg) of the polymer X.

More specifically, R in formula A3 relative to the total amount of structural units A contained in polymer X³⁴The structural unit that is a hydrogen atom is preferably 20 mass% or more.

In addition, R in the formula A3 in the structural unit A³⁴The content (content ratio: mass ratio) of the structural unit which is a hydrogen atom can be determined by¹³C-nuclear magnetic resonance spectroscopy (NMR) measurement and confirmation were performed according to the intensity ratio of peak intensities calculated by a usual method.

Further, as a preferable embodiment of the formulas A1 to A3, paragraphs 0044 to 0058 of International publication No. 2018/179640 can be referred to.

In the formulae 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, even more preferably a group having a tetrahydrofuran ring structure, and particularly preferably a tetrahydrofuranyl group, from the viewpoint of sensitivity.

The number of the structural units a contained in the polymer X may be 1, or 2 or more.

The content of the structural unit a in the polymer X is preferably 10 to 70% by mass, more preferably 15 to 50% by mass, and still more preferably 20 to 40% by mass, based on the total mass of the polymer components. If the range is within the above range, the resolution is further improved.

When the polymer X contains 2 or more kinds of the structural units a, the content of the structural unit a indicates the total content of the 2 or more kinds of the structural units a.

The content (content ratio: mass ratio) of the structural unit A in the polymer component can be determined by¹³C-NMR measurement and confirmation were carried out by calculating the intensity ratio of peak intensities according to a usual method.

Structural units B having acid groups

The polymer X may also contain a structural unit B having an acid group (simply referred to as "structural unit B").

An acid group of the structural unit B which is not protected by an acid-decomposable group is a structural unit containing an acid group having no protecting group. When the polymer X contains the structural unit B, the sensitivity at the time of pattern formation becomes good, and the polymer X becomes easily soluble in an alkaline developer in a developing step after pattern exposure, and the development time can be shortened.

The acid group in the present specification means a proton-dissociative group having a pKa of 12 or less.

From the viewpoint of improving the sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. Also, the pKa of the acid group is preferably-5 or more.

Examples of the acid group include a carboxyl group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group. Among them, a carboxyl group or a phenolic hydroxyl group is preferable, and a carboxyl group is more preferable.

The number of the structural units B contained in the polymer X may be only 1, or may be 2 or more.

The content of the structural unit B in the polymer X is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.1 to 5% by mass, based on the total mass of the polymer components. When the content is within the above range, the resolution is further improved.

When the polymer X contains 2 or more kinds of the structural units B, the content of the structural unit B represents the total content of 2 or more kinds of the structural units B.

The content (content ratio: mass ratio) of the structural unit B in the polymer X can be determined by¹³C-NMR measurement and confirmation were carried out by calculating the intensity ratio of peak intensities according to a usual method.

Other structural units C-

The polymer X preferably contains a structural unit C (simply referred to as "structural unit C") other than the structural unit a and the structural unit B described above, within a range that does not impair the effects of the photosensitive transfer material according to the present invention.

The monomer forming the structural unit C is not particularly limited, and examples thereof include styrenes, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, aryl (meth) acrylates, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic anhydrides, groups having an aliphatic cyclic skeleton, and other unsaturated compounds.

By using the structural unit C, at least one of the type and the content is adjusted, whereby various properties of the polymer X can be adjusted. In particular, the Tg, acid value, and hydrophilicity/hydrophobicity of the polymer X can be easily adjusted by including the structural unit C.

The polymer X may contain only 1 kind of the structural unit C, or may contain 2 or more kinds.

Specifically, the structural unit C includes structural units formed of styrene, α -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, or polymerized ethylene glycol monoacetoxyacetate mono (meth) acrylate. Further, compounds described in paragraphs 0021 to 0024 of Japanese patent laid-open No. 2004-264623 can be mentioned.

From the viewpoint of resolution, the structural unit C preferably contains a structural unit having a basic group.

Specific examples of the basic group include a group having a nitrogen atom such as an aliphatic amino group, an aromatic amino group, or a nitrogen-containing heteroaromatic ring group, and an aliphatic amino group is 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 a tertiary amino group is preferable.

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

In addition, the structural unit C is preferably a structural unit having an aromatic ring or a structural unit having an aliphatic ring skeleton, from the viewpoint of improving the electrical characteristics of the obtained transfer material. Specific examples of the monomer forming these structural units include styrene, α -methylstyrene, dicyclopentyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isoborne (meth) acrylate, and benzyl (meth) acrylate, and cyclohexyl (meth) acrylate is preferably used.

In addition, the monomer forming the structural unit C is preferably, for example, an alkyl (meth) acrylate from the viewpoint of adhesiveness. Among them, from the viewpoint of adhesion, an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is preferable. 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 is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less, based on the total mass of the polymer component. The lower limit is preferably 10% by mass or more, and more preferably 20% by mass or more. Within the above range, the resolution and the adhesion are further improved.

When the polymer component contains 2 or more kinds of the structural unit C, the content of the structural unit C represents the total content of 2 or more kinds of the structural unit C.

Preferred examples of the polymer X in the present invention will be described below, but the present invention is not limited to the examples below. The ratio of the structural units and the weight-average molecular weight in the following exemplary compounds can be appropriately selected in order to obtain preferable physical properties.

[ chemical formula 26]

Glass transition temperature of polymer X: tg-

From the viewpoint of transferability, the glass transition temperature (Tg) of the polymer X in the present invention is preferably 90 ℃ or lower, more preferably 20 ℃ or higher and 60 ℃ or lower, and further preferably 30 ℃ or higher and 50 ℃ or lower.

As a method for adjusting Tg of the polymer in the present invention to the above-described preferable range, Tg of a specific polymer to be targeted can be controlled based on FOX formula, for example, by Tg of a homopolymer of each structural unit of the polymer to be targeted and a mass ratio of each structural unit.

The following describes the formula FOX.

When Tg of the homopolymer of the 1 st structural unit contained in the polymer is Tg1, mass fraction of the copolymer of the 1 st structural unit is W1, Tg of the homopolymer of the 2 nd structural unit is Tg2, and mass fraction of the copolymer of the 2 nd structural unit is W2, Tg0(K) of the copolymer containing the 1 st structural unit and the 2 nd structural unit can be estimated from the following formula.

FOX formula: 1/Tg0 ═ W1/Tg1) + (W2/Tg2)

Acid value of the polymer X-

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

From the viewpoint of storage stability and adhesion between the photosensitive resin layer and the intermediate layer, the acid value of the polymer X is preferably 10mgKOH/g or less, and more preferably 3mgKOH/g or less.

The acid value of the polymer in the present invention is a value representing the mass of potassium hydroxide required for neutralizing 1g of the acidic component of the polymer. Specifically, a measurement sample was dissolved in a tetrahydrofuran/water (volume ratio) 9/1 mixed solvent, and the resulting solution was subjected to neutralization titration AT 25 ℃ with a 0.1mol/L aqueous sodium hydroxide solution using a potentiometric titration apparatus (product name: AT-510, KYOTO ELECTRONICS MANUFACTURING CO., LTD.). The acid value was calculated by the following formula, using the inflection point of the titration pH curve as the titration end point.

A＝56.11×Vs×0.1×f/w

A: acid value (mgKOH/g)

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

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

w: measuring the mass (g) of the sample (conversion of solid content)

Molecular weight of polymer X: mw-

The molecular weight of the polymer X is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight. By the weight average molecular weight of the polymer X being 60,000 or less, transfer at a low temperature (for example, 130 ℃ or less) can be achieved at the time of transferring the transfer material.

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

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

The weight average molecular weight of the polymer in the present invention can be measured by GPC (gel permeation chromatography), various commercially available apparatuses can be used as the measuring apparatus, and the contents of the apparatuses and the measuring techniques can be known ones.

As the measurement conditions, the sample concentration was 0.2 mass%, the flow rate was 0.35ml/min, the sample injection amount was 10 μ L, and the measurement temperature was 40 ℃.

Process for the preparation of polymers X

The method for producing the polymer X (synthesis method) is not particularly limited, but for example, it is synthesized by polymerizing a monomer for forming the structural unit a, and if necessary, a monomer for forming the structural unit B and a monomer for forming the structural unit C in an organic solvent using a polymerization initiator. Further, it can be synthesized by a so-called polymer reaction.

The content of polymer component or polymer X-

From the viewpoint of adhesion, the photosensitive resin layer in the present invention preferably contains the polymer component at a ratio of 50 to 99.9% by mass, more preferably 70 to 98% by mass, based on the total mass of the photosensitive resin layer.

From the viewpoint of adhesion, the photosensitive resin layer preferably contains the polymer X at a ratio of 50 to 99.9 mass%, more preferably 70 to 98 mass%, relative to the total mass of the photosensitive resin layer.

[ other Polymer ]

The photosensitive resin layer may contain, as a polymer component, a polymer (also referred to as "other polymer") that does not contain a structural unit having an acid group protected by an acid-decomposable group, within a range that does not impair the effect of the photosensitive transfer material according to the present invention, in addition to the polymer X.

The polymer component in the present invention means that other polymers added as necessary in addition to the polymer X are contained unless otherwise specified. Further, the compounds corresponding to the crosslinking agent, the dispersing agent and the surfactant described later are not included in the polymer component even if they are polymer compounds.

When the photosensitive resin layer contains another polymer, the content of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less, in the total polymer component.

The photosensitive resin layer may contain only 1 other polymer, or 2 or more polymers, in addition to the polymer X.

[ photoacid generators ]

The photosensitive resin layer preferably contains a photoacid generator.

The photoacid generator used in the present invention is a compound that can generate an acid by irradiation with actinic rays such as ultraviolet rays, far ultraviolet rays, X-rays, and electron beams.

The photoacid generator used in the present invention is preferably a compound that generates an acid by being sensitive to actinic rays having a wavelength of 300nm or more, preferably 300nm to 450nm, but the chemical structure is not limited. Further, even a photoacid generator which is not directly sensitive to actinic rays having a wavelength of 300nm or more can be used in combination with a sensitizer as long as it is a compound which is used together with the sensitizer to generate an acid by being sensitive to actinic rays having a wavelength of 300nm or more.

The photoacid generator used in the present invention 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 particularly preferably a photoacid generator that generates an acid having a pKa of 2 or less. The lower limit of pKa is not particularly limited, but is preferably at least-10.0, for example.

Examples of the nonionic photoacid generator include trichloromethyl s-triazine compounds, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds, and the like. Among these, the photoacid generator is preferably an oxime sulfonate compound from the viewpoint of sensitivity, resolution, and adhesion. Specific examples of the trichloromethyl-s-triazine, diazomethane compound and imide sulfonate compound include those described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494.

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

The photoacid generator preferably contains at least 1 compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and more preferably contains an oxime sulfonate compound, from the viewpoint of sensitivity and resolution.

Further, examples of a preferable photoacid generator include those having the following structures.

[ chemical formula 27]

The photosensitive resin layer may contain 1 kind of photoacid generator alone, or may contain 2 or more kinds.

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

[ other additives ]

The photosensitive resin layer in the present invention may contain other additives as necessary in addition to the polymer X, the photoacid generator, and the solvent.

As the other additives, known additives can be used, and examples thereof include a plasticizer, a sensitizer, a heterocyclic compound, an alkoxysilane compound, a basic compound, a rust inhibitor, and a surfactant.

Examples of the plasticizer, sensitizer, heterocyclic compound, and alkoxysilane compound include plasticizers, sensitizers, heterocyclic compounds, and alkoxysilane compounds described in paragraphs 0097 to 0119 of international publication No. 2018/179640.

The photosensitive resin layer in the photosensitive transfer material according to the present invention may contain a solvent. When the photosensitive resin layer is formed from a photosensitive resin composition containing a solvent, the solvent may remain.

The content of the solvent in the photosensitive resin layer is preferably 5% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less, with respect to the total mass of the photosensitive resin layer.

[ basic Compound ]

The photosensitive resin layer preferably further contains a basic compound.

The basic compound can be arbitrarily selected from among basic compounds used for chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include compounds described in paragraphs 0204 to 0207 of Japanese patent application laid-open publication No. 2011-221494, and the contents thereof are incorporated in the present specification.

Also, as the basic compound, N-cyclohexyl-N' - [2- (4-morpholinyl) ethyl ] thiourea (CMTU) can be preferably used. Further, as a commercial product of CMTU, there is exemplified CMTU manufactured by Toyo Kasei Kogyo co.

The basic compound is preferably a benzotriazole compound from the viewpoint of linearity of a conductive wiring when applied to formation of a conductive pattern.

The benzotriazole compound is not limited as long as it is a compound having 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-pyridyl) benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-ethylbenzotriazole, 1- (1 ' -hydroxyethyl) benzotriazole, 1- (2 ' -hydroxyethyl) benzotriazole, 1- (1 ' -hydroxymethyl) benzotriazole, and mixtures thereof, 1-propylbenzotriazole, 1- (1 ' -hydroxypropyl) benzotriazole, 1- (2 ' -hydroxypropyl) benzotriazole, 1- (3 ' -hydroxypropyl) benzotriazole, 4-hydroxy-1H-benzotriazole, 5-methyl-1H-benzotriazole, methylbenzotriazole-5-carboxylate, ethyl benzotriazole-5-carboxylate, tert-butyl benzotriazole-5-carboxylate, cyclopentylethyl benzotriazole-5-carboxylate, 1H-benzotriazole-1-acetonitrile, 1H-benzotriazole-1-carboxyaldehyde, 2-methyl-2H-benzotriazole, 2-ethyl-2H-benzotriazole and the like.

The photosensitive resin layer may contain 1 kind of the basic compound alone, or may contain 2 or more kinds.

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

Surfactants-

From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant.

Examples of the surfactant include anionic, cationic, nonionic (nonionic), and amphoteric surfactants. Preferred surfactants are nonionic surfactants.

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

Examples of the surfactant include surfactants described in paragraphs 0120 to 0125 of International publication No. 2018/179640.

As a commercially available surfactant, for example, MEGAFACE F-552 or F-554 (see above, DIC CORPORATION CO., LTD., manufactured by KOKAI CO., LTD.) can be used.

The photosensitive resin layer may contain 1 kind of surfactant alone, or may contain 2 or more kinds.

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

As other additives, known additives such as metal oxide particles, antioxidants, dispersants, acid proliferators, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, tackifiers, crosslinking agents, and organic or inorganic anti-settling agents can be added to the photosensitive resin layer in the present invention.

Preferred embodiments of these components are described in paragraphs 0165 to 0184 of Japanese patent application laid-open No. 2014-085643, the contents of which are incorporated in the present specification.

< average thickness of photosensitive resin layer >)

The average thickness of the photosensitive resin layer is preferably 0.5 to 20 μm. When the thickness of the 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 photosensitive resin layer is more preferably 0.8 to 15 μm, and particularly preferably 1.0 to 10 μm.

The method of measuring the average thickness of each layer in the present invention is a method of measuring the average thickness of each layer by observing a cross section in a direction perpendicular to the surface direction of the transfer material with a Scanning Electron Microscope (SEM). Then, the thickness at 10 or more points was measured as the average thickness, and the average value was set.

Method for forming photosensitive resin layer

The photosensitive resin layer in the present invention can be formed by preparing a photosensitive resin composition containing a component used for forming the photosensitive resin layer and a solvent, and coating and drying the composition. The composition can also be prepared by dissolving each component in a solvent in advance and then mixing the resulting solutions at a predetermined ratio. The composition prepared as described above can be filtered using, for example, a filter having a pore size of 0.2 to 30 μm.

The photosensitive resin layer in the present invention can be formed by applying the photosensitive resin composition to a temporary support or a cover film and drying the composition.

The coating method is not particularly limited, and coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.

Further, the photosensitive resin layer can be formed by forming an intermediate layer or another layer described later on the temporary support or the cover film.

[ photosensitive resin composition ]

The photosensitive resin composition preferably contains a component and a solvent used for forming the photosensitive resin layer. The photosensitive resin layer can be preferably formed by adjusting the viscosity by adding a solvent to each component, and applying and drying the mixture.

-solvent-

As the solvent, a known solvent can be used, and for example, the solvents described in paragraphs 0092 to 0094 of International publication No. 2018/179640 can be used.

Also, a solvent having a vapor pressure of 1kPa or more and 16kPa or less at 20 ℃ as described in paragraph 0014 of Japanese patent application laid-open No. 2018-177889 can be preferably used.

The solvent that can be used in the present invention may be used alone in 1 kind or 2 kinds in combination.

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

< temporary support >

The temporary support supports the photosensitive resin layer and is a releasable support.

The temporary support used in the present invention is preferably light-transmissive, from the viewpoint that the photosensitive resin layer can be exposed via the temporary support when the photosensitive resin layer is subjected to pattern exposure.

The average thickness of the temporary support is not particularly limited, but is preferably in the range of 5 to 200. mu.m, and more preferably in the range of 10 to 150 μm from the viewpoints of ease of handling, versatility, and the like.

< covering film >

In the photosensitive transfer material according to the present invention, it is preferable that the photosensitive transfer material has a cover film on a surface opposite to a surface on which the temporary support in the photosensitive transfer material is provided.

The cover film may be a resin film, paper, or the like, and is preferably a resin film in view of strength, flexibility, or the like. Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, polyethylene film, polypropylene film and polyethylene terephthalate film are preferable.

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

< other layer >

The photosensitive transfer material according to the present invention may have a layer other than the above (hereinafter, also referred to as "other layer"). Examples of the other layers include a contrast reinforcing layer and a thermoplastic resin layer.

Preferable embodiments of the contrast enhancing layer are described in paragraph 0134 of international publication No. 2018/179640, and preferable embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of japanese patent application laid-open No. 2014-085643, and preferable embodiments of the other layers are described in paragraphs 0194 to 0196 of japanese patent application laid-open No. 2014-085643, and the contents of these publications are incorporated in the present specification.

Here, an example of the layer structure of the photosensitive transfer material according to the present invention is schematically shown with reference to fig. 1.

The photosensitive transfer material 100 shown in FIG. 1 is formed by laminating a temporary support 12, a transfer layer 14 formed by laminating a photosensitive resin layer 14-1 and an intermediate layer 14-2, and a cover film 16 in this order. Hereinafter, the case where the present invention is described as a "transfer layer" indicates both of the photosensitive resin layer and the intermediate layer to be laminated.

(method for producing photosensitive transfer Material)

The method for producing the photosensitive transfer material according to the present invention is not particularly limited, and a known production method such as a known method for forming each layer can be used.

Among them, as a method for producing a photosensitive transfer material according to the present invention, a method comprising the steps of: a step of forming an intermediate layer by applying the intermediate layer-forming composition to a temporary support and drying the composition; and a step of forming a photosensitive resin layer by applying and drying the photosensitive resin composition on the intermediate layer.

The method for producing a photosensitive transfer material according to the present invention preferably further comprises a step of providing a cover film on the photosensitive resin layer after the step of forming the photosensitive resin layer.

(method for manufacturing resin pattern and method for manufacturing circuit wiring)

The method for producing a resin pattern according to the present invention is not particularly limited as long as it is a method for producing a resin pattern using the photosensitive transfer material according to the present invention, but preferably includes, in order, the steps of: a step of bringing an outermost layer on the side having the photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to the present invention into contact with a substrate and bonding the outermost layer to the substrate (hereinafter, sometimes referred to as "bonding step"); a step of pattern-exposing the photosensitive resin layer (hereinafter, may be referred to as an "exposure step"); and a step of forming a pattern by developing the exposed photosensitive resin layer (hereinafter, may be referred to as a "developing step").

In the method for manufacturing a resin pattern according to the present invention, the substrate is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on a surface thereof.

The method for manufacturing a circuit wiring according to the present invention may be a method using the photosensitive transfer material according to the present invention, but preferably includes the following steps in order: a step of bonding an outermost layer of the photosensitive transfer material according to the present invention on the side having the photosensitive resin layer with respect to the temporary support to a substrate having a conductive layer (hereinafter, sometimes referred to as "bonding step"); a step of pattern-exposing the photosensitive resin layer in the bonded photosensitive transfer material; a step of forming a resin pattern by developing at least the photosensitive resin layer having undergone pattern exposure; and a step of etching the substrate in a region where the resin pattern is not arranged (hereinafter, may be referred to as "etching step").

In the method for manufacturing a circuit wiring according to the present invention, the substrate is preferably a substrate having the conductive layer on a surface thereof.

In addition, the method for manufacturing a circuit wiring according to the present invention preferably includes a method of repeating the 4 steps of the bonding step, the exposure step, the developing step, and the etching step as 1 set a plurality of times.

In order to enable reuse (rework) of the substrate as described later, the method for manufacturing a circuit wiring according to the present invention preferably includes a method of performing the exposure step, the development step, and the etching step on the resin pattern after performing 4 steps of the bonding step, the exposure step, the development step, and the etching step.

The rework will be described below.

The photosensitive resin layer is a positive type that remains as an image in a portion that is not irradiated with actinic rays. In the positive photosensitive resin layer, the solubility of the exposed portion is improved by irradiation with actinic rays, for example, by using a photosensitive agent which generates an acid by irradiation with actinic rays, and therefore, when the pattern exposure time is short, both the exposed portion and the unexposed portion are not cured, and the obtained pattern shape is poor, the substrate can be reused (reworked) by blanket exposure or the like.

As an embodiment of the method for manufacturing the circuit wiring, international publication No. 2006/190405 can be referred to, and the contents thereof are incorporated in the present specification.

< bonding Process >

The method for producing a resin pattern according to the present invention or the method for producing a circuit wiring according to the present invention preferably includes a step (bonding step) of bringing an outermost layer of the photosensitive transfer material according to the present invention on the side having the photosensitive resin layer with respect to the temporary support into contact with a substrate, preferably a substrate having a conductive layer, and bonding the outermost layer to the substrate.

In the bonding step, the conductive layer is preferably pressure-bonded so as to be in contact with the outermost layer of the photosensitive transfer material according to the present invention on the side having the photosensitive resin layer with respect to the temporary support. In the above aspect, the photosensitive resin layer formed by patterning after exposure and development can be preferably used as an etching resist when etching the conductive layer.

The method for pressure-bonding the substrate and the photosensitive transfer material is not particularly limited, and a known transfer method and lamination method can be used.

Preferably, the outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer is superposed on the substrate, and the photosensitive transfer material and the substrate are bonded to each other by applying pressure and heat with a roller or the like. In the bonding, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator capable of improving productivity can be used. The method of manufacturing the circuit wiring according to the present invention is preferably performed by a roll-to-roll method. Therefore, the base material constituting the substrate is preferably a resin film.

Hereinafter, a roll-to-roll system will be described.

The roll-to-roll method is a method including: a step of unwinding the substrate or a structure including the substrate before any one of the steps included in the method for manufacturing the circuit wiring (also referred to as an "unwinding step"); and a step of spreading the substrate or the structure including the substrate after any one of the steps (also referred to as a "winding step"), and a mode of performing at least any one of the steps (preferably all of the steps or all of the steps except the heating step) while conveying the substrate or the structure including the substrate.

The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and a known method may be used in a manufacturing method using a roll-to-roll method.

The substrate used in the present invention is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface of a base material.

The substrate may have a conductive layer on a base material such as glass, silicon, or a thin film, and an arbitrary layer may be formed as necessary.

The substrate is preferably transparent.

The refractive index of the base material is preferably 1.50 to 1.52.

When a resin film substrate is used as the substrate, a substrate having a small optical strain and a substrate having high transparency are more preferably used. Specific examples of the raw material include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

In the substrate having a conductive layer on a base material, a film base material is preferable from the viewpoint of roll-to-roll manufacturing. When the method for manufacturing a circuit wiring according to the present invention is a circuit wiring for a touch panel, the base material is preferably a sheet-like resin composition.

As the conductive layer formed on the substrate, any conductive layer used for a general circuit wiring or a touch panel wiring can be given.

The conductive layer is preferably at least 1 layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and particularly preferably a copper layer or a silver layer, from the viewpoint of conductivity and thin line formability.

The substrate may have 1 conductive layer or 2 or more conductive layers. When the number of layers is 2 or more, conductive layers having different materials are preferable.

Examples of the material of the conductive layer include a metal and a conductive metal oxide.

Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.

Examples of the conductive metal Oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO (silicon Oxide)₂In addition, "conductivity" in the present invention means that the volume resistivity is less than 1 × 10⁶Omega cm, preferably having a volume resistivity of less than 1 × 10⁴Ωcm。

In the method for manufacturing a circuit wiring according to the present invention, when a plurality of conductive layers are used on a substrate, at least one of the plurality of conductive layers preferably contains a conductive metal oxide.

< Exposure Process >

The method for manufacturing a resin pattern according to the present invention or the method for manufacturing a circuit wiring according to the present invention preferably includes a step (exposure step) of pattern-exposing the photosensitive resin layer after the step of bonding.

The detailed arrangement and specific dimensions of the patterns in the present invention are not particularly limited. From the viewpoint of improving the display quality of a display device (for example, a touch panel) provided with an input device having circuit wiring manufactured by the method for manufacturing circuit wiring according to the present invention and reducing the area occupied by the extraction wiring as much as possible, at least a part of the pattern (particularly, an electrode pattern of the touch panel and a part of the extraction wiring) is preferably a thin line of 100 μm or less, and more preferably a thin line of 70 μm or less.

The light source used for exposure may be appropriately selected and used as long as it irradiates light (for example, 365nm, 405nm, etc.) in a wavelength range capable of exposing the photosensitive resin layer. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, an LED (Light Emitting Diode), and the like can be given.

The exposure amount is preferably 5mJ/cm²～200mJ/cm²More preferably 10mJ/cm²～100mJ/cm²。

In the exposure step, the pattern exposure may be performed after the temporary support is peeled from the photosensitive resin layer, or the pattern exposure may be performed through the temporary support before the temporary support is peeled, and then the temporary support is peeled. In order to prevent contamination of the mask due to contact between the photosensitive resin layer and the mask and to avoid an influence of foreign matter adhering to the mask on exposure, it is preferable to perform pattern exposure without peeling the temporary support. The pattern exposure may be exposure through a mask or may be direct exposure using a laser or the like.

< developing Process >

The method for manufacturing a resin pattern according to the present invention or the method for manufacturing a circuit wiring according to the present invention preferably includes a step (developing step) of forming a resin pattern by developing the exposed photosensitive resin layer after the exposing step.

In the case where the photosensitive transfer material has an intermediate layer, the intermediate layer in the exposed portion is also removed together with the exposed photosensitive resin layer in the developing step. In the developing step, the intermediate layer in the unexposed portion may be removed so as to be dissolved or dispersed in the developer.

The photosensitive resin layer exposed in the developing step may be developed using a developer.

The developing solution is not particularly limited as long as it can remove the non-image portion of the photosensitive resin layer, and a known developing solution such as the developing solution described in japanese patent application laid-open No. 5-072724 can be used. The developer is preferably a developer in which an exposed portion (positive type) of the photosensitive resin layer is subjected to a dissolution type developing operation. For example, the developer is preferably an aqueous alkaline developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05mol/L (liter) to 5 mol/L. The developer may further contain a water-soluble organic solvent, a surfactant, and the like. As a developer that can be preferably used in the present invention, for example, a developer described in paragraph 0194 of international publication No. 2015/093271 can be cited.

The developing method is not particularly limited, and any of spin-on immersion development, shower and spin development, immersion development, and the like can be used. Note that, when the shower development is described, the exposed portion can be removed by blowing a developing solution into the exposed photosensitive resin layer by shower. After development, it is preferable to remove the development residue while blowing a cleaning agent or the like by showering and wiping with a brush or the like. The liquid temperature of the developing solution is preferably 20 to 40 ℃.

Further, the method may further include a baking step after the pattern including the photosensitive resin layer obtained by development is subjected to a heat treatment.

The post-baking is preferably heated in an environment of 8.1kPa to 121.6kPa, and more preferably in an environment of 50.66kPa or more. On the other hand, it is more preferably carried out under an environment of 111.46kPa or less, and particularly preferably carried out under an environment of 101.3kPa or less.

Further, other steps such as a post-exposure step may be provided before the etching step described later.

< etching Process >

The method for manufacturing a circuit wiring according to the present invention preferably includes a step (etching step) of etching the substrate in a region where the resin pattern is not arranged.

In the etching step, the conductive layer is etched using the pattern formed by the photosensitive resin layer in the developing step as an etching resist.

As a method of the etching treatment, a known method such as a method described in paragraphs 0048 to 0054 of jp 2010-152155 a, a method based on dry etching such as a known plasma etching, and the like can be applied.

For example, as a method of the etching treatment, a wet etching method in which the substrate is immersed in an etching solution is generally performed. The etching solution used for wet etching may be an acidic type or an alkaline type, as appropriate, depending on the object to be etched.

Examples of the acidic etching solution include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid alone, and mixed aqueous solutions of acidic components and salts such as ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a component in which a plurality of acidic components are combined.

The temperature of the etching solution is not particularly limited, but is preferably 45 ℃ or lower. The resin pattern used as an etching mask (etching pattern) in the present invention preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ℃. Therefore, the photosensitive resin layer is prevented from being peeled off in the etching step, and a portion where the photosensitive resin layer is not present is also selectively etched.

After the etching step, a cleaning step of cleaning the substrate subjected to the etching treatment and a drying step of drying the cleaned substrate may be performed as necessary in order to prevent contamination of the production line.

< removal Process >

The method for manufacturing a circuit wiring according to the present invention preferably performs a step of removing the resin pattern (removal step).

The removal step is not particularly limited and may be performed as needed, but is preferably performed after the etching step.

The method of removing the residual photosensitive resin layer is not particularly limited, but a method of removing by means of medicine treatment can be mentioned, and the use of a removing liquid can be particularly preferred.

The method for removing the photosensitive resin layer includes a method of immersing the substrate having the photosensitive resin layer or the like in a removing solution which is preferably stirred at 30 to 80 ℃, more preferably at 50 to 80 ℃ for 1 to 30 minutes.

Examples of the removing solution include a solution obtained by dissolving an inorganic base component such as sodium hydroxide or potassium hydroxide or an organic base component such as a primary amine compound, a secondary amine compound, a tertiary amine compound or a quaternary ammonium salt compound in water, dimethyl sulfoxide, N-methylpyrrolidone or a mixed solution thereof.

The removal liquid may be used to remove the metal oxide particles by a spraying method, a shower method, a spin coating method, or the like.

< full exposure of photosensitive resin layer >

Before the removal step, it is preferable to include a step of blanket-exposing the photosensitive resin layer (also referred to as a "blanket-exposure step"). A step of heating the photosensitive resin layer subjected to blanket exposure (also referred to as a "heating step") may be included as necessary. The blanket exposure step and the heating step are preferably performed after the etching step and before the removal step.

After the etching step, the photosensitive resin layer used as an etching mask is subjected to blanket exposure, whereby the solubility in and the permeability of the removing solution are improved, and the removing solution is excellent even when used for a long time. In addition, when the heating step is included, the reaction rate of the photoacid generator and the reaction rate of the generated acid with the positive photosensitive resin can be further increased by the heating step, and as a result, the removal performance can be improved.

The light source used for the exposure in the blanket exposure step 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 blanket exposure step is preferably 5mJ/cm from the viewpoint of removability²～1,000mJ/cm²More preferably 10mJ/cm²～800mJ/cm²Particularly preferably 100mJ/cm²～500mJ/cm²。

The exposure amount in the blanket exposure step is preferably not less than the exposure amount in the exposure step, and more preferably more than the exposure amount in the exposure step, from the viewpoint of removability.

< other working procedures >

The method of manufacturing a circuit wiring according to the present invention may include any process (other process) other than the above. For example, the following steps are included, but the present invention is not limited to these steps.

Further, as examples of the exposure step, the development step, and other steps in the present invention, the methods described in paragraphs 0035 to 0051 of jp 2006-023696 can also be preferably used in the present invention.

Peeling process of covering film

The method for manufacturing a resin pattern according to the present invention or the method for manufacturing a circuit wiring according to the present invention preferably includes a step of peeling off the cover film of the photosensitive transfer material when the photosensitive transfer material according to the present invention has the cover film (may be referred to as a "cover film peeling step"). The method for peeling the cover film is not limited, and a known method can be applied.

< Process for reducing reflectance of visible ray >

Examples of the treatment for reducing the visible light reflectance include oxidation treatment. For example, the visible light reflectance can be reduced by performing an oxidation treatment on copper to form copper oxide and blackening the copper oxide.

Preferable embodiments of the treatment for reducing the visible light reflectance are described in paragraphs 0017 to 0025 of jp 2014-150118 a and paragraphs 0041, 0042, 0048 and 0058 of jp 2013-206315 a, the contents of which are incorporated in the present specification.

< Process for Forming insulating film, Process for Forming New conductive layer on insulating film >

The method for manufacturing a circuit wiring according to the present invention preferably further includes a step of forming an insulating film on the formed circuit wiring and a step of forming a new conductive layer on the insulating film.

In the method for manufacturing a circuit wiring according to the present invention, it is also preferable that a circuit is formed sequentially or simultaneously on the conductive layers formed on both surfaces of the base material using a substrate having a plurality of conductive layers on both surfaces of the base material. With these configurations, a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface and a second conductive pattern is formed on the other surface of the base material can be formed. Further, it is also preferable that the circuit wiring for a touch panel having these structures is formed from both surfaces of the base material in a roll-to-roll manner.

The circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention can be applied to various devices. Examples of the device including the circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention include an input device, and the like, and preferably a touch panel, and more preferably an electrostatic capacitance type touch panel. The input device can be applied to display devices such as organic EL display devices and liquid crystal display devices.

(method of manufacturing touch Panel)

The method for manufacturing a touch panel according to the present invention may be a method using the photosensitive transfer material according to the present invention, but preferably includes the following steps in order: a step (bonding step) of bringing an outermost layer on the side having the photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to the present invention into contact with a substrate having a conductive layer and bonding the outermost layer to the substrate; a step (exposure step) of pattern-exposing the photosensitive resin layer; a step (developing step) of developing the exposed photosensitive resin layer to form a resin pattern; and a step (etching step) of etching the substrate in a region where the resin pattern is not arranged.

As described above with respect to the "method for manufacturing circuit wiring" according to the present invention, the preferred embodiments of the method for manufacturing a touch panel according to the present invention, such as the specific embodiments of the respective steps and the order of performing the respective steps, are the same.

In addition to the above, a known method for manufacturing a touch panel can be used as the method for manufacturing a touch panel according to the present invention.

The method of manufacturing a touch panel according to the present invention may include any process (other process) other than the above process.

Fig. 3 and 4 show an example of a mask pattern used in the method for manufacturing a touch panel according to the present invention.

In pattern a shown in fig. 3 and pattern B shown in fig. 4, SL and G are non-image portions (light-shielding portions), and DL is a frame body for dummy display alignment. In the method of manufacturing a touch panel according to the present invention, for example, a touch panel in which circuit wirings having patterns a corresponding to SL and G are formed can be manufactured by exposing a photosensitive resin layer through a mask having the pattern a shown in fig. 3. Specifically, the preparation can be carried out by the method described in FIG. 1 of International publication No. 2016/0190405. In an example of the touch panel manufactured, G is a portion where a transparent electrode (electrode for touch panel) is formed, and SL is a portion where a wiring of the peripheral extraction portion is formed.

The detection method in the touch panel according to the present invention may be any of known methods such as a resist film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the electrostatic capacitance system is preferable.

Examples of the Touch panel type include a so-called in-cell type (for example, as described in fig. 5, 6, 7, and 8 of japanese patent laid-open No. 2012-517051), a so-called out-cell type (for example, as described in fig. 19 of japanese patent laid-open No. 2013-168125, and as described in fig. 1 and 5 of japanese patent laid-open No. 2012-089102), an OGS (One Glass Solution) type, a TOL (Touch-on-Lens) type (for example, as described in fig. 2 of japanese patent laid-open No. 2013-054727), other structures (for example, as described in fig. 6 of japanese patent laid-open No. 2013-164), and various out-cell types (for example, so-called GG, G1 · G2, GFF, GF2, GF1, G1F, and the like).

Examples of the touch panel according to the present invention include those described in paragraph 0229 of japanese patent application laid-open No. 2017-120345.

Examples

The embodiments of the present invention will be described in further detail below with reference to examples. The materials, the amounts used, the ratios, the contents of the processes, the order of the processes, 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 specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass. The "maximum absorption wavelength" in the present embodiment means a maximum absorption wavelength in a wavelength range of 400nm to 780nm in color development.

(examples and comparative examples of photosensitive transfer Material according to embodiment 1 of the present invention)

Abbreviations related to components used in examples represent the following compounds, respectively.

-an intermediate layer-

[ Polymer (adhesive Polymer for intermediate layer) ]

Polymer B-11: nisso HPC-SSL (hydroxypropyl cellulose NIPPON SODA CO., LTD. manufactured)

Polymer B-12: METOLOSE 60SH-03 (hydroxypropyl methylcellulose, Shin-Etsu chemical Co., Ltd., manufactured by Ltd.)

[ coloring matter ]

A-1: bromophenol blue (manufactured by FUJIFILM Wako Pure Chemical Corporation, maximum absorption wavelength: 606nm, water-soluble)

A-2: bromocresol green (water-soluble with maximum absorption wavelength: 626nm, manufactured by FUJIFILM Wako Pure Chemical Corporation)

A-3: VPB-NAPS (naphthalene sulfonate of Victoria pure blue) (Hodogaya Chemical Co., Ltd., maximum absorption wavelength: 616nm, water-soluble)

E-to confirm the presence or absence of pH sensitivity of pigment

The pH sensitivity of the color development of the above-mentioned dye in the aqueous solution was confirmed by the following method.

100mL of a mixed solution of 0.1g of a dye dissolved in ethanol and water (ethanol/water 1/2[ mass ratio ]) was added with 0.1mol/l (1N) of a hydrochloric acid aqueous solution to adjust the pH to 1. Titration was carried out with 0.01mol/l (0.01N) aqueous sodium hydroxide solution, and a change in color development and pH at which the color development was changed were confirmed. The results are shown below.

In addition, the pH was measured at 25 ℃ using a pH meter (model: HM-31, manufactured by DKK-TOA CORPORATION).

A-1: above pH4.0, the color development (i.e., the maximum absorption wavelength) changes.

A-2: above pH5.4, the color development (i.e., the maximum absorption wavelength) changes.

A-3: in the pH range of 1-14, even if the pH is changed, the color development (i.e., the maximum absorption wavelength) is not changed.

[ pH adjusting agent ]

G-1: 0.1N aqueous sodium hydroxide solution (manufactured by FUJIFILM Wako Pure Chemical Corporation)

G-2: 0.1N aqueous solution of potassium hydroxide (manufactured by FUJIFILM Wako Pure Chemical Corporation)

G-3: 0.1N aqueous lithium hydroxide solution (manufactured by FUJIFILM Wako Pure Chemical Corporation)

G-4: tetrabutylammonium hydroxide (40% by mass aqueous solution) (manufactured by FUJIFILM Wako Pure chemical corporation)

G-5: hexadecyltrimethylammonium hydroxide (10 mass% aqueous solution) (manufactured by FUJIFILM Wako pure chemical Corporation)

G-6: choline (50% by mass aqueous solution) (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

G-7: benzyltrimethylammonium hydroxide (40% by mass methanol solution) (manufactured by FUJIFILM Wako Pure chemical corporation)

[ inorganic Filler ]

H-1: SNOWTEX O (manufactured by Nissan Chemical Industries, LTD.)

H-2: SNOWTEX C (manufactured by Nissan Chemical Industries, LTD.)

H-3: SNOWTEX N (manufactured by Nissan Chemical Industries, LTD.)

[ surfactant ]

E-11: MEGAFACE F-444(DIC CORPORATION CO., LTD. manufactured)

Resist layer-

[ Polymer ]

In the following examples, the following abbreviations denote the following compounds, respectively.

ATHF: 2-tetrahydrofuran acrylic ester (synthetic product)

MATHF: 2-tetrahydrofuran methacrylate (synthetic product)

ATHP: tetrahydro-2H-pyran-2-yl acrylate (Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.)

MATHP: tetrahydro-2H-pyran-2-yl methacrylate (Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.)

MAEVE: 1-ethoxymethacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

TBMA: t-butyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

AA: acrylic acid (Tokyo Chemical Industry Co., Ltd.)

MAA: methacrylic acid (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

EA: ethyl acrylate (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

MMA: methyl methacrylate (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

CHA: cyclohexyl acrylate (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

CHMA: cyclohexyl methacrylate (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

N-propyl acetate (Showa Denko Co., Ltd.)

V-601: dimethyl-2, 2' -azobis (methyl 2-propionate) (manufactured by FUJIFILM Wako Pure chemical corporation)

Synthesis of-ATHF-

Acrylic acid (72.1 parts, 1.0 molar equivalent), hexane (72.1 parts) was added to the three-necked flask and cooled to 20 ℃. After dropwise addition of camphorsulfonic acid (0.00070 parts by mass, 0.003 mmol) and 2-dihydrofuran (70.1 parts by mass, 1.0 mol), the mixture was stirred at 20 ℃. + -. 2 ℃ for 1.5 hours, and then heated to 35 ℃ and stirred for 2 hours. KYOWARD200 (aluminum hydroxide adsorbent, Kyowa Chemical Industry co., manufactured by ltd.) and KYOWARD1000 (hydrotalcite-based adsorbent, Kyowa Chemical Industry co., manufactured by ltd.) were sequentially spread on a suction filter, and then the reaction solution was filtered, thereby obtaining a filtrate. Hydroquinone monomethyl ether (MEHQ, 0.0012 parts) was added to the obtained filtrate, followed by concentration under reduced pressure at 40 ℃, whereby 140.8 parts of tetrahydrofuran-2-yl acrylate (ath) was obtained as a colorless oil (yield 99.0%).

Synthesis of MATHF

Methacrylic acid (86.0 parts, 1.0 molar equivalent), hexane (72.1 parts) was added to the three-necked flask and cooled to 20 ℃. After dropwise addition of camphorsulfonic acid (0.00070 parts by mass, 0.003 mmol) and 2-dihydrofuran (70.1 parts by mass, 1.0 mol), the mixture was stirred at 20 ℃. + -. 2 ℃ for 1.5 hours, and then heated to 35 ℃ and stirred for 2 hours. KYOWARD200 (aluminum hydroxide adsorbent, Kyowa Chemical Industry co., manufactured by ltd.) and KYOWARD1000 (hydrotalcite-based adsorbent, Kyowa Chemical Industry co., manufactured by ltd.) were sequentially spread on a suction filter, and then the reaction solution was filtered, thereby obtaining a filtrate. Hydroquinone monomethyl ether (MEHQ, 0.0012 parts) was added to the obtained filtrate, followed by concentration under reduced pressure at 40 ℃, whereby 152.9 parts of tetrahydrofuran-2-yl Methacrylate (MATHF) were obtained as a colorless oil (yield 98.0%).

Synthesis example of Polymer B-1

N-propyl acetate (75.0 parts) was added to a three-necked flask, and the temperature was raised to 90 ℃ under a nitrogen atmosphere. A solution prepared by mixing ATHF (38.70 parts), AA (1.47 parts), CHA (59.83 parts), V-601(4.1 parts) and n-propyl acetate (75.0 parts) was added dropwise to a three-necked flask solution maintained at 90 ℃. + -. 2 ℃ over 2 hours. After completion of the dropwise addition, the mixture was stirred at 90 ℃. + -. 2 ℃ for 2 hours, whereby a solution of polymer B-1 (solid content concentration: 40.0 mass%) was obtained.

Examples of Synthesis of polymers B-2 to B-8

Polymers B-2 to B-8 were synthesized in the same manner as in the synthesis of polymer A-1 under the other conditions by changing the kind of monomers as shown in Table 1 below.

The solid content concentration of each polymer was 40 mass%.

In addition, the mark of "-" in table 1 indicates that the component is not included.

[ Table 1]

[ photoacid generators ]

C-1: a compound having a structure shown below (synthesized by the method described in paragraph 0227 of Japanese patent laid-open publication No. 2013-047765)

[ chemical formula 28]

C-2: a compound having a structure shown below (synthesized by a method described in paragraph 0210 of Japanese patent laid-open No. 2014-197155)

[ chemical formula 29]

C-3: the following Compound (Irgacure PAG-103, manufactured by BASF corporation)

[ chemical formula 30]

C-4: CPI-310TS (triaryl sulfide salt, San-Apro Ltd.)

[ basic Compound ]

D-1: a compound having a structure shown below (CMTU)

[ chemical formula 31]

D-2: 2,4, 5-Triphenylimidazole (Tokyo Chemical Industry Co., Ltd., manufactured by Ltd.)

D-3: 1, 5-diazabicyclo [4.3.0] -5-nonene (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

[ surfactant ]

E-1: f-552 (fluorine-based nonionic surfactant, DIC CORPORATION CO., LTD. manufactured)

E-2: f-554 (fluorine-based nonionic surfactant, DIC CORPORATION CO., LTD. manufactured)

(example 1)

< preparation of intermediate layer composition 1 >

The following components were mixed and filtered through a polytetrafluoroethylene filter having a pore size of 5.0 μm, thereby preparing an intermediate layer composition 1.

Water: 891.5 parts by mass

Methanol: 891.5 parts by mass

Polymer B-11: 80.0 parts by mass

Pigment A-1: 1.2 parts by mass

pH adjuster G-1: 35.8 parts by mass

Inorganic filler H-1: 100.0 parts by mass

Surfactant E-11: 0.05 part by mass

< preparation of resist layer composition 1 >

The following components were mixed and filtered through a polytetrafluoroethylene filter having a pore size of 1.0 μm, thereby preparing a resist layer composition 1.

MEK (methyl ethyl ketone: Maruzen Petrochemical Co., Ltd.): 306.0 parts by mass

N-propyl acetate (Showa Denko co., ltd.): 459.9 parts by mass

Polymer B-1 solution: 423.5 parts by mass

Photoacid generator C-1: 9.00 parts by mass

Basic compound D-1: 1.35 parts by mass

Surfactant E-1: 0.24 parts by mass

< preparation of photosensitive transfer Material >

An intermediate layer composition 1 having a dry film thickness of 1.8 μm was applied to a polyethylene terephthalate film (hereinafter also referred to as "PET (a)") having a thickness of 16 μm as a temporary support by using a slit nozzle. Thereafter, it was dried in a convection oven at 100 ℃ for 2 minutes.

On the formed intermediate layer, resist layer composition 1 was applied using a slit nozzle in an amount such that the dry film thickness became 3.0 μm. Finally, a polypropylene film (Oji F-Tex Co., Ltd., ALPHAN PK-002) was pressure-bonded as a cover film to prepare a photosensitive transfer material.

(examples 2 to 27 and 201)

The dye, the polymer, the pH adjuster, the inorganic filler, and the surfactant were dissolved and mixed in a mixed solvent of water and methanol (water/methanol: 891.5 parts by mass/891.5 parts by mass) so as to be added in amounts shown in table 2 below, and the mixture was filtered through a polytetrafluoroethylene filter having a pore size of 1.0 μm, thereby preparing intermediate layer compositions 2 to 18.

An intermediate layer composition 19 was prepared in the same manner as the intermediate layer composition 1, except that 2.0 parts by mass of the photoacid generator C-4 was further added as shown in table 3.

Then, the polymer, the photoacid generator, the basic compound, the surfactant, and other components were dissolved and mixed in a mixed solvent of n-propyl acetate and methyl ethyl ketone (n-propyl acetate/methyl ethyl ketone: 70/30[ vol.%) so as to have a solid content ratio (mass ratio) shown in table 4 below, and the solid content concentration was adjusted to 14 mass%, and filtration was performed using a filter made of polytetrafluoroethylene having a pore diameter of 1.0 μm, thereby preparing resist layer compositions 2 to 10.

Then, the following components were mixed and filtered through a polytetrafluoroethylene filter having a pore size of 1.0 μm, thereby preparing a resist layer composition 11.

A 41 mass% (solid content) MEK (methyl ethyl ketone) solution of a copolymer having a composition of methacrylic acid/styrene/benzyl methacrylate (polymerization ratio 30/20/50), an acid equivalent amount of 290, and a weight average molecular weight of 55000: 55.0 parts by mass

Dimethacrylate of polyethylene glycol obtained by adding ethylene oxide in an average amount of 5 moles to each end of bisphenol A (Shin-Nakamura Chemical Co, Ltd., BPE-500): 25.0 parts by mass

A dimethacrylate of a polyalkylene glycol obtained by adding an average of 12 moles of propylene oxide to a polypropylene glycol and an average of 3 moles of ethylene oxide to both ends: 20.0 parts by mass

4, 4' -bis (diethylamino) benzophenone: 0.1 part by mass

2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer: 3.0 parts by mass

Diamond green: 0.1 part by mass

Colorless crystal violet: 0.3 part by mass

In example 1, a photosensitive transfer material was produced in the same manner as in example 1 except that the intermediate layer composition 1 was replaced with the intermediate layer compositions 2 to 19, respectively, and the resist layer composition 1 was replaced with the resist layer compositions 2 to 11, respectively.

Comparative example 1

In example 1, a photosensitive transfer material of comparative example 1 was produced in the same manner as in example 1 except that the intermediate layer composition 1 was replaced with a comparative intermediate layer composition 1 prepared without adding the coloring matter a-1 and the pH adjusting agent G-1 used for the preparation of the intermediate layer composition 1.

Comparative example 2

A dye, a polymer, a pH adjuster, an inorganic filler, and a surfactant were dissolved and mixed in a mixed solvent of water and methanol (water/methanol: 891.5 parts by mass/891.5 parts by mass) so as to be added in amounts shown in table 2 below, and the mixture was filtered through a polytetrafluoroethylene filter having a pore size of 1.0 μm, thereby preparing comparative intermediate layer composition 2.

A photosensitive transfer material was produced in the same manner as in example 1, except that in example 1, the intermediate layer composition 1 was replaced with the comparative intermediate layer composition 2.

Comparative example 3

In example 201, a photosensitive transfer material was produced in the same manner as in example 201 except that a comparative intermediate layer composition 3 prepared without adding the dye a-1 and the photoacid generator C-4 used for the preparation of the intermediate layer composition 19 was used instead of the intermediate layer composition 19 as shown in table 3.

[ Table 2]

[ Table 3]

[ Table 4]

[ Performance evaluation 1]

A copper layer-attached polyethylene terephthalate (PET) substrate was used, in which a copper layer was formed on a PET film having a thickness of 100 μm by a sputtering method at a thickness of 200 nm.

< visibility >

The produced photosensitive transfer material was laminated on a PET substrate with a copper layer under lamination conditions of a roll temperature of 90 ℃, a line pressure of 0.8MPa and a line speed of 3.0m/min. The temporary support of the photosensitive transfer material was brought into contact with a glass mask having a line-to-space pattern (Duty ratio 1:1) with a line width of 10 μm without peeling off the temporary support, and passed through the mask and an ultrahigh pressure mercury lamp at 200mJ/cm²The resist layer is exposed to light at the exposure amount of (1). After standing for 4 hours, the exposed line and space patterns were observed by an optical microscope and evaluated according to the following evaluation criteria.

< evaluation criteria >

A: it was confirmed that the line and space patterns could be discriminated with sufficient color density.

B: no line and space patterns were identified.

[ Table 5]

	Intermediate layer	Resist layer	Visibility
				Example 1	Intermediate layer composition 1	Resist layer composition 1	A
Example 2	Intermediate layer composition 2	Resist layer composition 1	A
				Example 3	Intermediate layer composition 3	Resist layer composition 1	A
Example 4	Interlayer composition 4	Resist layer composition 1	A
				Example 5	Intermediate layer composition 5	Resist layer composition 1	A
Example 6	Interlayer composition 6	Resist layer composition 1	A
				Example 7	Interlayer composition 7	Resist layer composition 1	A
Example 8	Intermediate layer composition 8	Resist layer composition 1	A
				Example 9	Interlayer composition 9	Resist layer composition 1	A
Example 10	Interlayer composition 10	Resist layer composition 1	A
				Example 11	Intermediate layer composition 11	Resist layer composition 1	A
Example 12	Intermediate layer composition 12	Resist layer composition 1	A
				Example 13	Intermediate layer composition 13	Resist layer composition 1	A
Example 14	Intermediate layer composition 14	Resist layer composition 1	A
				Example 15	Interlayer composition 15	Resist layer composition 1	A
Example 16	Intermediate layer composition 16	Resist layer composition 1	A
				Example 17	Intermediate layer composition 17	Resist layer composition 1	A
Example 18	Interlayer composition 18	Resist layer composition 1	A
				Example 19	Intermediate layer composition 1	Resist layer composition 2	A
Example 20	Intermediate layer composition 1	Resist layer composition 3	A
				Example 21	Intermediate layer composition 1	Resist layer composition 4	A
Examples22	Intermediate layer composition 1	Resist layer composition 5	A
				Example 23	Intermediate layer composition 1	Resist layer composition 6	A
Example 24	Intermediate layer composition 1	Resist layer composition 7	A
				Example 25	Intermediate layer composition 1	Resist layer composition 8	A
Example 26	Intermediate layer composition 1	Resist layer composition 9	A
				Example 27	Intermediate layer composition 1	Resist layer composition 10	A
Example 201	Interlayer composition 19	Resist layer composition 11	A
				Comparative example 1	Comparative intermediate layer composition 1	Resist layer composition 1	B
Comparative example 2	Comparative intermediate layer composition 2	Resist layer composition 1	B
				Comparative example 3	Comparative interlayer composition 3	Resist layer composition 11	B

(examples 28 to 33)

In example 1, a photosensitive transfer material was produced in the same manner as in example 1 except that the intermediate layer composition and the resist layer composition were changed to the structures shown in table 6 below.

[ Performance evaluation 2]

< adhesion >

A copper-clad polyethylene terephthalate (PET) substrate was used in which a copper layer was formed on a PET film having a thickness of 100 μm by a sputtering method at a thickness of 200 nm.

The photosensitive transfer material thus prepared was cut into a size of 50cm × 50cm to prepare a sample sheet, and the coating film of the sample sheet thus obtained was peeled off and laminated on a copper-clad PET film under lamination conditions of a roll temperature of 90 ℃, a line pressure of 1.0MPa, and a line speed of 4.0m/min. Next, the temporary support was peeled off, the portions of the intermediate layer and the resist layer adhering to the copper layer were scaled with an oil pen, the entire PET substrate was photographed, and the areas of the portions of the intermediate layer and the resist layer adhering to the copper layer and the entire sample piece were calculated by image analysis software (ImageJ (National institute of health). The area ratio was obtained from the following formula, and the evaluation was performed according to the following evaluation criteria.

Area ratio (%) — area where intermediate layer and resist layer were attached/area of the entire sample piece × 100

< evaluation criteria >

5: more than 95 percent

4: more than 90 percent and less than 95 percent

3: more than 85 percent and less than 90 percent

2: more than 80 percent and less than 85 percent

1: less than 80 percent

[ Table 6]

	Intermediate layer	Resist layer	Adhesion Property
				Example 28	Intermediate layer composition 13	Resist layer composition 3	1
Example 29	Intermediate layer composition 14	Resist layer composition 3	3
				Example 30	Interlayer composition 15	Resist layer composition 3	4
Example 31	Intermediate layer composition 16	Resist layer composition 3	5
				Example 32	Intermediate layer composition 17	Resist layer composition 3	3
Example 33	Interlayer composition 18	Resist layer composition 3	3

(example 101)

On a 100 μm thick PET substrate, Indium Tin Oxide (ITO) was formed as a conductive layer of the 2 nd layer by sputtering to a thickness of 150nm, and on top of that, copper was formed as a conductive layer of the 1 st layer by vacuum evaporation to a thickness of 200nm, thereby producing a circuit-forming substrate.

The photosensitive transfer material 1 obtained in example 1 was laminated on the copper layer (line pressure 0.8MPa, line speed 3.0m/min, roll temperature 90 ℃ C.). The contact pattern exposure was performed using a photomask provided with a pattern (hereinafter, also referred to as "pattern a") shown in fig. 3 having a structure in which the conductive layer sheets were connected in one direction, without peeling the temporary support.

In the pattern a shown in fig. 3, the solid line portion SL and the gray line portion G are light-shielding portions, and the dotted line portion DL is a frame which virtually indicates alignment.

After that, the temporary support is peeled off, and development and water washing are performed to obtain a pattern a. Next, after the copper layer was etched using a copper etching solution (KANTO CHEMICAL co., manufactured by inc., product Cu-02), the ITO layer was etched using an ITO etching solution (KANTO CHEMICAL co., manufactured by inc., product ITO-02), thereby obtaining a substrate in which copper (solid line portion SL) and ITO (gray portion G) were drawn together in a pattern a.

Next, pattern exposure was performed using a mask in which openings of the pattern shown in fig. 4 (hereinafter, also referred to as "pattern B") were provided in an aligned state, and development and water washing were performed.

In pattern B shown in fig. 4, gray portion G is a light shielding portion, and dotted portion DL is a frame virtually indicating alignment.

Thereafter, the copper layer was etched using Cu-02, and the remaining resist layer was peeled off using a peeling solution (10 mass% aqueous sodium hydroxide solution), thereby obtaining a circuit wiring board.

Thus, a circuit wiring board was obtained. As a result of observation with a microscope, there were no peeling, defects, and the like, and a clear pattern was obtained.

(example 102)

ITO was deposited on a 100 μm thick PET substrate by sputtering to a thickness of 150nm as a 2 nd conductive layer, and copper was deposited thereon by vacuum deposition to a thickness of 200nm as a 1 st conductive layer, thereby producing a circuit forming substrate.

The photosensitive transfer material 1 obtained in example 1 was laminated on the copper layer (line pressure 0.8MPa, line speed 3.0m/min, roll temperature 90 ℃ C.).

The resist layer was pattern-exposed using a photomask provided with a pattern a shown in fig. 3 having a structure in which conductive layer sheets were connected in one direction without peeling off the temporary support. After that, the temporary support is peeled off, and development and water washing are performed to obtain a pattern a. Next, after the copper layer was etched using a copper etching solution (KANTO CHEMICAL co., inc. made Cu-02), the ITO layer was etched using an ITO etching solution (KANTO CHEMICAL co., inc. made ITO-02), thereby obtaining a substrate in which copper (solid line portion SL) and ITO (gray portion G) were drawn together in a pattern a.

Subsequently, PET (a) was laminated on the remaining resist as a protective layer. In this state, pattern exposure was performed using a photomask in which the openings of the pattern B shown in fig. 4 were aligned, and after peeling off PET (a), development and washing were performed.

Thereafter, the copper wiring was etched using Cu-02, and the remaining resist layer was peeled off using a peeling liquid (KANTO CHEMICAL co., inc.

As a result of observation with a microscope, there were no peeling, defects, and the like, and a clear pattern was obtained.

(examples and comparative examples of photosensitive transfer Material according to embodiment 2 of the present invention)

< Synthesis of Polymer >

In the following synthesis examples, the following abbreviations represent the following compounds, respectively.

ATHF: 2-tetrahydrofuran acrylic ester (synthetic product)

AA: acrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

EA: ethyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

MMA: methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

CHA: cyclohexyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

PMPMPMMA: methacrylic acid 1,2,2,6, 6-pentamethyl-4-piperidine (manufactured by FUJIFILM Wako Pure chemical corporation)

Synthesis of "ATHF

The synthesis was carried out according to paragraph 0172 of International publication No. 2018/115192.

< Synthesis example of Polymer A-1 >)

Isopropyl acetate (75.0 parts) was added to a three-necked flask and the temperature was raised to 90 ℃ under a nitrogen atmosphere. A solution prepared by adding ATHF (30.0 parts), MMA (40.0 parts), EA (30.0 parts), V-601(4.0 parts) and isopropyl acetate (75.0 parts) to a three-necked flask solution maintained at 90 ℃. + -. 2 ℃ was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred at 90 ℃. + -. 2 ℃ for 2 hours, whereby polymer A-1 (solid content concentration: 40.0%) was obtained.

Synthesis examples of polymers A-2 to A-6

The polymer was synthesized in the same manner as in the polymer a-1 under the other conditions by changing the kind of monomers as shown in table 7 below. The solid content concentrations of the polymers A-2 to A-6 were 40% by mass, respectively.

The unit of the amount of the monomer in table 7 is mass%, and the amount ratio of each structural unit in the obtained polymer is also the same.

[ Table 7]

The weight-average molecular weights of the polymers A-1 to A-6 were 20,000, respectively.

< photoacid generators >

B-1: a compound having a structure shown below (which is a compound described in paragraph 0227 of Japanese patent laid-open publication No. 2013-047765 and synthesized by the method described in paragraph 0227.)

[ chemical formula 32]

< basic Compound >

C-1: 1,2, 3-benzotriazole (Tokyo Chemical Industry Co., Ltd., manufactured by Ltd.)

C-2: N-cyclohexyl-N' - [2- (4-morpholinyl) ethyl ] thiourea (CMTU, Toyo Kasei Kogyo Co., Ltd., manufactured by Ltd.)

< surfactant >

E-1: MEGAFACE F-552 (fluorosurfactant, DIC CORPORATION CO., LTD. manufactured)

< preparation of photosensitive resin compositions 1 to 6 >

Photosensitive resin compositions 1 to 6 were obtained by dissolving and mixing a polymer, a photoacid generator, a basic compound, and a surfactant in isopropyl acetate so that the solid content concentration became 15 mass%, and filtering the mixture with a polytetrafluoroethylene filter having a pore diameter of 0.2 μm, respectively, so as to obtain solid content ratios shown in table 8 below.

[ Table 8]

The unit of the amount of each component in table 8 is part by mass.

< preparation of composition 1 for Forming intermediate layer >

An intermediate layer-forming composition 1 was prepared by the following formulation.

Production of 10% solution of hydroxypropyl cellulose (HPC)

Distilled water: 45.0 portion

Methanol: 45.0 portion

Hydroxypropyl cellulose (product name: Nisso HPC-SSL, NIPPON SODA CO., LTD.): 10.0 parts of

After dissolving the above components at room temperature (25 ℃), the solution was filtered through a 3 μm filter (manufactured by profile II NIHON fill ltd), thereby obtaining an HPC 10% solution.

Production of composition 1 for Forming intermediate layer

The intermediate layer-forming composition 1 was obtained by dissolving and mixing the components according to the following formulation.

Distilled water: 7.1 parts of

Methanol: 53.1 parts

HPC 10% solution: 29.7 parts

SNOWTEX O (silica particles, Nissan Chemical Industries, LTD, Ltd., average particle diameter 12 nm): 10.0 parts of

MEGAFACE F-444 (fluorosurfactant, DIC CORPORATION CO., LTD.): 0.01 part

N-octyltrimethylammonium chloride (Tokyo Chemical Industry co., ltd.): 0.02 portion

< preparation of composition for intermediate layer formation 2 to 30 >

The components shown in table 9, such as particles, were changed as shown in table 9 below, and compositions 2 to 30 for forming an intermediate layer were prepared by the same method as that for composition 1 for forming an intermediate layer under the other conditions.

[ Table 9]

The following shows the details of the abbreviations listed in table 9, except for those described above.

HPC: hydroxypropyl cellulose (product name: HPC-SSL, NIPPON SODA CO., LTD. manufactured)

HMPC: hydroxypropyl methylcellulose (product name: TC-5, Shin-Etsu Chemical Co., Ltd., manufactured by Ltd.)

SNOWTEX O: silica particles, Nissan Chemical Industries, LTD., manufactured by Ltd., arithmetic average particle diameter of 12nm, surface state anionicity (silanol)

SNOWTEX XS: silica particles, Nissan Chemical Industries, LTD., manufactured by Ltd., arithmetic mean particle diameter of 5nm, surface state anionicity (silanol)

SNOWTEX OS: silica particles, Nissan Chemical Industries, LTD., manufactured by Ltd., arithmetic mean particle diameter 9nm, surface state anionicity (silanol)

SNOWTEX O-40: silica particles, Nissan Chemical Industries, LTD., manufactured by Ltd., arithmetic mean particle diameter 22nm, surface state anionicity (silanol)

SNOWTEX OL: silica particles, Nissan Chemical Industries, LTD., manufactured by Ltd., arithmetic mean particle diameter of 45nm, surface state anionicity (silanol)

SNOWTEX OYL: silica particles, Nissan Chemical Industries, LTD., manufactured by Ltd., arithmetic mean particle diameter of 60nm, surface state anionicity (silanol)

OTAC: n-octyl trimethyl ammonium chloride

DDTAC: n-dodecyl trimethyl ammonium chloride

HDTAC: n-hexadecyltrimethylammonium chloride

HDPyC: n-hexadecylpyridinium chloride

BMSAC: benzyldimethyl stearyl ammonium chloride hydrate (Tokyo Chemical Industry Co., Ltd., manufactured by Ltd.)

HDDSAH: hexadecyldimethyl (3-sulfopropyl) ammonium hydroxide intramolecular salt (manufactured by Tokyo chemical industry Co., Ltd.)

BZC: benzethonium chloride (Tokyo Chemical Industry Co., Ltd., the compound of the following structure)

HDTAH: n-hexadecyl trimethyl ammonium hydroxide

HDTA: n-hexadecyl trimethyl amine

BTAH: benzyl trimethyl ammonium hydroxide

BPB: bromophenol blue (colorant, manufactured by FUJIFILM Wako Pure Chemical Corporation, maximum absorption wavelength: 606nm)

[ chemical formula 33]

(example 2-1)

< production of photosensitive transfer Material >

As shown in Table 10 below, the intermediate layer-forming composition 1 was applied to a 30 μm thick polyethylene terephthalate film as a temporary support using a slit nozzle so that the application width became 1.0m and the film thickness became 1.8 μm, and the intermediate layer was formed in a 100 ℃ dry region over 40 seconds. Then, the photosensitive resin composition A-1 was applied onto the intermediate layer using a slit nozzle so that the application width became 1.0m and the film thickness became 3 μm, and the resultant was passed through a drying zone at 100 ℃ for 40 seconds to form a photosensitive resin layer. A polyethylene film (OSM-N, manufactured by Tredegar Corporation) was pressure-bonded as a cover film (protective film) to the photosensitive resin layer to prepare a photosensitive transfer material 2-1, and the photosensitive transfer material 2-1 was wound to prepare a roll system.

(example 2-2 to 2-27)

Photosensitive transfer materials 2-2 to 2-27 were produced in the same manner as in example 2-1, except that the compositions shown in Table 10 below were used.

Comparative examples 2-1 to 2-4

Photosensitive transfer materials 2-C1 to 2-C4 were produced in the same manner as in example 2-1, except that the compositions shown in Table 10 below were used.

(examples 2-28 to 2-32)

Photosensitive transfer materials 2-28 to 2-32 were produced in the same manner as in example 2-1, except that water-soluble resin layers were formed using the compositions shown in Table 11 below, and then intermediate layers were formed in the same manner as the water-soluble resin layers. In addition, in the formation of the water-soluble resin layer, the descriptions in table 11 of the intermediate layer-forming compositions prepared above were used as the water-soluble resin layer-forming compositions.

Further, the results of observing the cross-sectional SEM of the photosensitive transfer materials produced in examples 2-28 to 2-32 confirmed that the following 4 layers were formed: temporary support/water-soluble resin layer (water-soluble resin layer) having a particle content of 5 mass% or less/layer (intermediate layer) containing particles, the polar compound, and the water-soluble resin/photosensitive resin layer. Further, it was confirmed that the above-mentioned polar compound was contained in the intermediate layer as a result of observing the cross section of the photosensitive transfer material of examples 2-28 to 2-32 obtained by the SIMS method.

The photosensitive transfer materials 2-1 to 2-32 and 2-C1 to 2-C4 thus obtained were used for the following evaluation.

< evaluation of Properties >

A polyethylene terephthalate (PET) substrate having a copper-containing layer formed on a PET film having a thickness of 100 μm by vacuum deposition to a thickness of 200nm was used.

Evaluation of adhesion between the intermediate layer and the photosensitive resin layer-

The cover film was peeled from the photosensitive transfer material of example 2-1, and the obtained photosensitive transfer material was laminated on the copper layer of the above-mentioned copper layer-attached PET substrate at 100 ℃ and at a speed of 4m/min and a linear pressure of 0.6MPa, and then the temporary support was peeled off, thereby producing a laminate in which a positive photosensitive layer was laminated on the copper layer.

A test piece having a cross-cut of 25 squares of cuts was made by using a cutter blade to add 6 cuts at 1mm intervals to the extent of reaching the base material and also to add 6 cuts at 1mm intervals in a straight line. The transparent adhesive tape was bonded thereto, and the transparent adhesive tape was peeled off in a direction of 90 degrees to observe the adhesion area, whereby the adhesion between the intermediate layer and the photosensitive resin layer was evaluated according to the following evaluation criteria. The practical range is 2 or more.

[ evaluation standards ]

3: the stripping area is less than 30 percent

2: the stripping area is more than 30 percent and less than 90 percent

1: the peeling area is more than 90%

Evaluation of storage stability

The produced photosensitive transfer material was developed under lamination conditions of a roll temperature of 120 ℃, a line pressure of 1.0MPa and a line speed of 0.5m/min, and then laminated on the above copper-clad PET substrate. The temporary support was not peeled off, and was exposed to light via a line-and-space pattern mask (Duty ratio 1:1) having a line width of 10 μm by an ultrahigh pressure mercury lamp, left at 23 ℃ under 55% RH for 3 hours, and then peeled off to be developed. For development, development was carried out for 30 seconds by shower development using a 1.0% sodium carbonate aqueous solution at 25 ℃.

When a line-and-space pattern of 10 μm was formed by the above method, the residue in the space portion was observed by a Scanning Electron Microscope (SEM), and the exposure amount was determined so that the resist line width became exactly 10 μm.

The produced photosensitive transfer material was left to stand at 40 ℃ and 55% RH for 7 days, and then laminated on a PET substrate with a copper layer under the same conditions as described above. Without peeling off the temporary support, the resist was exposed to light with an exposure dose at which the resist line width determined by the above method became exactly 10 μm through a line and space pattern mask (Duty ratio 1:1) with a line width of 10 μm, left at 23 ℃ under 55% RH for 3 hours, and then the temporary support was peeled off and developed. For development, development was carried out for 30 seconds by shower development using a 1.0% sodium carbonate aqueous solution at 25 ℃.

The line widths of the obtained line and the space pattern were observed by a Scanning Electron Microscope (SEM), the line widths of 50 points in total were measured for 5 lines, the variation in line width from 10 μm was obtained, the average value of the obtained values was calculated, and the average value was evaluated by the following criteria. The smaller the average value of the variation in line width from 10 μm, the more excellent the storage stability, and the average value of the variation in line width from 10 μm is preferably less than 1.5 μm.

[ evaluation standards ]

3: less than 1.0 μm

2: 1.0 μm or more and less than 1.5 μm

1: 1.5 μm or more

Evaluation of liquid stability

After storing the composition for forming an intermediate layer at 30 ℃ for 7 days, the change in filtration pressure at the time of filtration of 100L was recorded at a flow rate of 150mL/min using a 1-inch cassette polypropylene filter (Profile II, manufactured by NIHON PALL LTD.) having a pore size of 3 μm, and the liquid stability was evaluated according to the following evaluation criteria.

In examples 28 to 32, both of the 2 intermediate layer-forming compositions used were evaluated, and the evaluation of the defects is shown in table 5.

[ evaluation standards ]

3: the initial filtration pressure is 0.1MPa or less, and the filtration pressure change at the filtration of 100L is less than 0.01 MPa.

2: the initial filtration pressure is 0.1MPa or less, and the filtration pressure change at the time of filtration of 10L is 0.01MPa or more and less than 0.05 MPa.

1: the initial filtration pressure is a value exceeding 0.1MPa or the filtration pressure change at 10L filtration is 0.05MPa or more.

The evaluation results are shown in table 10 or table 11.

[ Table 10]

[ Table 11]

As is clear from table 10, the photosensitive transfer materials of the examples have better adhesion between the intermediate layer and the photosensitive resin layer than the photosensitive transfer material of the comparative example.

Further, as is clear from table 11, by also producing a water-soluble resin layer, the intermediate layer and the photosensitive resin layer were excellent in adhesion, storage stability, and liquid stability.

Even if the storage stability or the liquid stability is evaluated to be 1, the photosensitive transfer material or the intermediate layer-forming composition can be used without any problem in practice by using it without storing it for a long period of time from the time of production.

(examples 2 to 101)

A circuit-forming substrate was prepared by forming ITO as a 2 nd conductive layer by sputtering on a 100 μm thick PET substrate to form ITO with a thickness of 150nm, and forming copper as a 1 st conductive layer by vacuum deposition on the ITO substrate to form copper with a thickness of 200 nm.

The protective film was peeled off from the copper layer, and the photosensitive transfer material obtained in example 2-1 (laminating roller temperature 100 ℃, linear pressure 0.8MPa, linear velocity 3.0m/min.) was laminated on a substrate to prepare a laminate. The obtained laminate was subjected to contact pattern exposure using a photomask provided with a pattern a shown in fig. 3 having a structure in which conductive layer pads are connected in one direction without peeling the temporary support. A high-pressure mercury lamp having i-ray (365nm) as the main wavelength of exposure was used for the exposure.

After that, the temporary support is peeled off, and development and water washing are performed to obtain a pattern a. Next, after the copper layer was etched using a copper etching solution (KANTO CHEMICAL co., manufactured by inc., product Cu-02), the ITO layer was etched using an ITO etching solution (KANTO CHEMICAL co., manufactured by inc., product ITO-02), thereby obtaining a substrate in which copper was drawn in a pattern a together with ITO.

Subsequently, the same temporary support as in example 2-1 was laminated on the remaining resist as a protective layer. In this state, alignment was performed, pattern exposure was performed using a mask having an opening portion provided with the pattern B, and after the temporary support was peeled off, development and water washing were performed. Thereafter, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a peeling liquid (KANTO CHEMICAL co., inc.

The obtained circuit wiring board was observed with a microscope, and was free from peeling, defects, and the like, and had a clear pattern.

(examples 2 to 102)

After a substrate having a pattern A was obtained in the same manner as in examples 2 to 101, the protective film was peeled off, and the photosensitive transfer material obtained in example 1 was attached again to the remaining resist under the same conditions as in examples 2 to 101. The temporary support was not peeled off in an aligned state, pattern exposure was performed using a mask having an opening portion of the pattern B, and then the temporary support was peeled off, and development and water washing were performed to obtain the pattern B. Next, under the same conditions as in examples 2 to 101, the copper wiring was etched and the remaining photosensitive resin layer was peeled off, thereby obtaining a circuit wiring substrate having a conductive pattern.

The disclosures of japanese patent application No. 2018-018478, applied on 5/2/2018, japanese patent application No. 2018-098329, applied on 22/5/2018, japanese patent application No. 2018-162138, applied on 30/8/2018, and japanese patent application No. 2019-016912, applied on 1/2/2019, the entire contents of which are incorporated herein by reference.

All documents, patent applications, and technical standards described in the present specification are incorporated by reference into the present specification to the same extent as if each document, patent application, and technical standard was specifically and individually described to be incorporated by reference.

Claims

1. A photosensitive transfer material comprising a temporary support, an intermediate layer and a resist layer in this order,

the intermediate layer contains the following component (A),

(A) the components: a dye which has a maximum absorption wavelength of 450nm or more in a wavelength range of 400 to 780nm during color development and in which the maximum absorption wavelength is changed by an acid, an alkali or a radical.

2. The photosensitive transfer material according to claim 1,

the coloring matter as the component (A) is a pH sensitive coloring matter.

3. The photosensitive transfer material according to claim 1 or 2,

the colorant as the component (A) has a triarylmethane skeleton.

4. The photosensitive transfer material according to any one of claims 1 to 3, wherein,

the pigment as the component (A) contains at least 1 selected from the group consisting of a pigment represented by the following formula I, an open ring body of a pigment represented by the following formula I, and a neutralizer of the open ring body,

in the formula I, Ar and Ar' independently represent an aromatic group, R¹、R²、R³And R⁴Each independently represents a hydrogen atom or a substituent having a valence of 1.

5. The photosensitive transfer material according to any one of claims 1 to 4, wherein,

the resist layer contains the following components (B) and (C),

(C) The components: a photoacid generator.

6. The photosensitive transfer material according to claim 5,

7. The photosensitive transfer material according to claim 6,

The maximum absorption wavelength in the wavelength range of 400nm to 780nm in the color development of the dye as the component (A) is shortened by an acid emitted from the photoacid generator as the component (C) by exposure.

8. The photosensitive transfer material according to any one of claims 5 to 7, wherein,

the acid generated from the photoacid generator as the component (C) is phosphoric acid or sulfonic acid, and is an acid having a pKa of 4 or less.

9. The photosensitive transfer material according to any one of claims 5 to 8, wherein,

the structural unit having a group in which the acid group is protected with an acid-decomposable group, which is contained in the polymer as the component (B), is a structural unit represented by the following formula II,

in the formula II, R¹And R²Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R¹And R²Any of which is alkyl or aryl, R³Represents alkyl or aryl, R¹Or R²Optionally with R³Linked to form a cyclic ether, R⁴Represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group.

10. The photosensitive transfer material according to any one of claims 1 to 9, wherein,

the intermediate layer further contains the following component (G),

(G) the components: a pH adjusting agent.

11. The photosensitive transfer material according to claim 10,

The pH regulator is quaternary ammonium salt.

12. The photosensitive transfer material according to any one of claims 1 to 11,

the resist layer further contains the following (D) component,

(D) the components: a basic compound.

13. A method of manufacturing a circuit wiring, comprising in sequence:

bonding the photosensitive transfer material according to any one of claims 1 to 12 to a substrate so that the resist layer of the photosensitive transfer material is in contact with the substrate;

a step of pattern-exposing the resist layer of the photosensitive transfer material after the step of bonding;

a step of forming a pattern by developing the resist layer after the step of exposing the pattern; and

and a step of etching the substrate in the region where the pattern is not arranged.

14. A method of manufacturing a touch panel, comprising in order: