WO2019151534A1 - Matériau de transfert photosensible, procédé de fabrication de câblage de circuit, et procédé de fabrication d'écran tactile - Google Patents

Matériau de transfert photosensible, procédé de fabrication de câblage de circuit, et procédé de fabrication d'écran tactile Download PDF

Info

Publication number
WO2019151534A1
WO2019151534A1 PCT/JP2019/004043 JP2019004043W WO2019151534A1 WO 2019151534 A1 WO2019151534 A1 WO 2019151534A1 JP 2019004043 W JP2019004043 W JP 2019004043W WO 2019151534 A1 WO2019151534 A1 WO 2019151534A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
transfer material
mass
acid
photosensitive transfer
Prior art date
Application number
PCT/JP2019/004043
Other languages
English (en)
Japanese (ja)
Inventor
山田　悟
知樹 松田
藤本　進二
克己 篠田
壮二 石坂
漢那　慎一
一真 両角
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2018162138A external-priority patent/JP6832899B2/ja
Priority claimed from JP2019016912A external-priority patent/JP7007308B2/ja
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to CN201980011644.1A priority Critical patent/CN111684359A/zh
Publication of WO2019151534A1 publication Critical patent/WO2019151534A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

Definitions

  • the present disclosure relates to a photosensitive transfer material, a circuit wiring manufacturing method, and a touch panel manufacturing method.
  • a display device such as an organic electroluminescence (EL) display device and a liquid crystal display device
  • a touch panel such as a capacitance type input device
  • an electrode pattern corresponding to a sensor of a visual recognition part a wiring of a peripheral wiring part
  • a wiring of a lead-out wiring part A conductive layer pattern such as is provided inside the touch panel.
  • the formation of a patterned layer requires a small number of steps for obtaining a required pattern shape.
  • a method of developing after exposure through a mask having the following pattern is widely used.
  • JP 2011-25532 A As a film with a metal film used for manufacturing a conventional circuit board, a film described in JP 2011-25532 A is known.
  • JP 2011-25532 A has a support, a nano-inorganic filler-containing water-soluble polymer release layer formed on the support, and a metal film layer formed on the release layer.
  • a film with a metal film is described.
  • the dye as component (A) is pH sensitive
  • the photosensitive transfer material according to ⁇ 1> which is a dye.
  • the dye as the component (A) contains at least one selected from a dye represented by the following formula I, a ring-opened product of the dye represented by the following formula I, and a neutralized product of the ring-opened product ⁇
  • the photosensitive transfer material according to any one of 1> to ⁇ 3>.
  • Ar and Ar ′ each independently represent an aromatic group.
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a monovalent substituent.
  • ⁇ 6> The maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of coloring of the dye as the component (A) is changed by the acid released from the photoacid generator as the component (C) by exposure.
  • ⁇ 7> The photosensitivity according to ⁇ 6>, wherein the maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of coloring of the dye as component (A) is shortened from the acid released from the (C) photoacid generator upon exposure.
  • Transfer material. ⁇ 8> The acid generated from the photoacid generator as component (C) is phosphoric acid or sulfonic acid, and the pKa is 4 or less, or any one of ⁇ 5> to ⁇ 7> Photosensitive transfer material.
  • the structural unit having a group in which the polymer as the component (B) has an acid group protected by an acid-decomposable group is a structural unit represented by the following formula II ⁇ 5> to ⁇ 8>
  • R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R 1 and R 2 is an alkyl group or an aryl group, and R 3 is an alkyl group Alternatively, it represents an aryl group, and R 1 or R 2 and R 3 may be linked to form a cyclic ether.
  • R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group.
  • (G) Component: pH adjusting agent ⁇ 11> The photosensitive transfer material according to ⁇ 10>, wherein the pH adjusting agent is a quaternary ammonium salt. ⁇ 12> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 11>, wherein the resist layer further contains the following component (D).
  • a step of bonding the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 12> to the substrate while bringing the resist layer of the photosensitive transfer material into contact with the substrate, and a step of bonding A step of pattern exposing the resist layer of the subsequent photosensitive transfer material; a step of developing the resist layer after the pattern exposing step to form a pattern; and a step of etching the substrate in a region where the pattern is not disposed. , In this order.
  • a step of bonding the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 12> to the substrate while bringing the resist layer of the photosensitive transfer material into contact with the substrate, and a step of bonding A step of pattern exposing the resist layer of the subsequent photosensitive transfer material; a step of developing the resist layer after the pattern exposing step to form a pattern; and a step of etching the substrate in a region where the pattern is not disposed.
  • the manufacturing method of the touch panel which contains these in this order.
  • the intermediate layer includes a water-soluble resin, particles, an acidic group, a basic group, an anionic group, and a cationic group.
  • a photosensitive transfer material comprising a polymer containing a structural unit, wherein the photosensitive resin layer and the intermediate layer are in contact with each other.
  • ⁇ 2-3> The photosensitive transfer material according to ⁇ 2-1> or ⁇ 2-2>, wherein the acid value of the polymer is 3 mgKOH / g or less.
  • the polar group is a primary to tertiary amino group or a primary to quaternary ammonium group.
  • the photosensitive transfer material as described.
  • ⁇ 2-5> The photosensitive property according to any one of ⁇ 2-1> to ⁇ 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. Transfer material.
  • ⁇ 2-6> The photosensitive transfer material according to any one of ⁇ 2-1> to ⁇ 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> to ⁇ 2-7>, wherein the arithmetic average particle diameter of the particles is 30 nm or less.
  • ⁇ 2-9> Any one of ⁇ 2-1> to ⁇ 2-8>, further comprising a water-soluble resin layer having a particle content of 5% by mass or less between the temporary support and the intermediate layer.
  • the photosensitive transfer material as described in one.
  • ⁇ 2-10> a step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of ⁇ 2-1> to ⁇ 2-9> into contact with a substrate and bonding the substrate; and the photosensitive resin layer
  • a method for producing a resin pattern which includes a step of pattern exposure and a step of developing the exposed photosensitive resin layer to form a pattern in this order.
  • ⁇ 2-11> a step of bonding the photosensitive resin layer of the photosensitive transfer material according to any one of ⁇ 2-1> to ⁇ 2-9> in contact with a substrate having a conductive layer; A step of pattern exposing the photosensitive resin layer, a step of developing the exposed photosensitive resin layer to form a pattern, and a step of etching a conductive layer in a region where the pattern is not disposed.
  • a circuit wiring manufacturing method including this order.
  • ⁇ 2-12> a step of bonding the photosensitive resin layer of the photosensitive transfer material according to any one of ⁇ 2-1> to ⁇ 2-9> in contact with a substrate having a conductive layer; A step of pattern exposing the photosensitive resin layer, a step of developing the exposed photosensitive resin layer to form a pattern, and a step of etching a conductive layer in a region where the pattern is not disposed. Manufacturing method of touch panel including in this order.
  • a photosensitive transfer material that is excellent in visibility of an exposed portion and an unexposed portion.
  • FIG. 1 is a schematic diagram illustrating an example of a layer configuration of a photosensitive transfer material according to the present disclosure.
  • FIG. 2 is a schematic diagram illustrating an example of a method for manufacturing a circuit wiring for a touch panel using the photosensitive transfer material according to the present disclosure.
  • FIG. 3 is a schematic diagram showing the pattern A.
  • FIG. 4 is a schematic diagram showing the pattern B.
  • symbol may be abbreviate
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • an upper limit value or a lower limit value described in a numerical range may be replaced with an upper limit value or a lower limit value in another numerical range.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
  • the amount of each component in the composition is the total amount of the plurality of corresponding substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
  • the term “process” is included in the term as long as the intended purpose of the process is achieved, even when the process is not clearly distinguished from other processes.
  • the notation that does not indicate substitution and non-substitution includes those having no substituent and those having a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the chemical structural formula in the present disclosure may be described as a simplified structural formula in which a hydrogen atom is omitted.
  • “mass%” and “weight%” are synonymous, and “part by mass” and “part by weight” are synonymous.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are columns of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation).
  • the molecular weight is detected by a gel permeation chromatography (GPC) analyzer used and detected by a solvent THF (tetrahydrofuran) and a differential refractometer and converted using polystyrene as a standard substance.
  • GPC gel permeation chromatography
  • the first embodiment of the photosensitive transfer material according to the present disclosure has an intermediate layer and a resist layer in this order on a temporary support, and the intermediate layer has a wavelength range of 400 nm during color development as the component (A).
  • a maximum absorption wavelength of ⁇ 780 nm is 450 nm or more, and a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical is contained.
  • a photosensitive transfer material that is a dry film resist is required to have visibility of an exposed portion from the viewpoint of confirmation of the exposed portion.
  • it is known to introduce a color former into the resist layer, but there are concerns about various adverse effects.
  • the present inventors have found that a photosensitive transfer material can be provided in which the concern about various adverse effects is reduced by introducing the coloring mechanism into the intermediate layer instead of the resist layer.
  • the photosensitive transfer material of the present disclosure can suppress the occurrence of coloring or decoloring of the dye in the unexposed area, and can cause the coloring or decoloring of the dye only in the exposed area. As a result, it becomes easy to visually distinguish and distinguish between a portion where color development or decoloration has occurred and a portion where color development or decoloration has not occurred, and it is assumed that excellent visibility is obtained.
  • a material for example, a photoacid generator described later
  • the photosensitive transfer material in the present disclosure may be a so-called negative photosensitive transfer material in which the removability in development is reduced by exposure, or the so-called positive photosensitivity in which the removability in development is increased by exposure. It may be a transfer material. 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 disclosure can be an NQD-based photosensitive transfer material using NQD (naphthoquinone diazide).
  • NQD naphthoquinone diazide
  • naphthoquinone diazide for example, naphthoquinone diazide described in paragraph 0201 of JP-A No. 2004-126047 can be used.
  • a novolak resin is included.
  • the novolak resin for example, the novolak resin described in paragraph 0201 of JP-A-2004-126047 can be used.
  • the intermediate layer according to the present disclosure contains a dye (component (A)) that has a maximum absorption wavelength of 450 nm or more in a wavelength range of 400 nm to 780 nm at the time of color development, and whose maximum absorption wavelength is changed by an acid, a base, or a radical.
  • middle layer is a layer formed with the intermediate
  • middle layer contains the pigment
  • the intermediate layer described in paragraphs 0084 to 0087 of JP-A-2005-259138 can be used.
  • the intermediate layer is preferably one that is dispersed or dissolved in water or an aqueous alkali solution.
  • the intermediate layer of the photosensitive transfer material according to the present disclosure has a maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development of 450 nm or more, and contains a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical.
  • the maximum absorption wavelength is changed by an acid, base or radical when the dye is in a state where the dye in a colored state is decolored by an acid, base or radical, and the dye in a decolored state is colored by an acid, base or radical It may refer to any of the embodiments in which the dye in a colored state changes to a colored state in another hue.
  • the coloring matter may be a compound that changes color from a decolored state upon exposure, or a compound that changes color from a colored state upon exposure.
  • it may be a dye whose color development or decoloring state is changed by introducing an acid, a base or a radical into the composition by exposure, and by introducing an acid, a base or a radical, the properties in the system (
  • it may be a dye whose coloring or decoloring state changes when pH) changes.
  • it may be a dye that changes its color development or decoloration state by being directly applied as a stimulus with acid, base or radical without exposure.
  • a compound that is decolored by exposure is preferable, and a latent dye that is decolored by an acid generated from a photoacid generator, that is, the pH is changed by the generation of an acid to be decolored. More preferably a pH sensitive dye.
  • Confirmation of the pH-sensitive dye can be performed by the following method.
  • Titrate with a 0.01 mol / l (0.01 N) aqueous sodium hydroxide solution to confirm the color change and the pH at which the color change appears.
  • the pH is a value measured at 25 ° C. using a pH meter (model number: HM-31, manufactured by Toa DKK).
  • Examples of the coloring mechanism of the dye in the present disclosure may include the following aspects.
  • a photoacid generator, a photobase generator or a photoradical generator is added to the intermediate layer, and after exposure, an acid-reactive dye or a base-reactive dye is generated by the acid, base or radical generated from the photoacid generator or the like after exposure.
  • a radical reactive dye for example, a water-soluble leuco dye
  • develops color in particular, in the case of a chemically amplified positive-type photosensitive transfer material, the following modes may be employed.
  • 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. Then, an acid-reactive dye (for example, a water-soluble leuco dye) is colored by the generated acid.
  • the dye has a maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development of 450 nm or more, and from the viewpoint of visibility, is preferably 550 nm or more, more preferably 550 nm to 700 nm, and more preferably 550 nm to 650 nm. More preferably. Further, the dye may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development, or may have two or more.
  • the maximum absorption wavelength at the time of color development having the highest absorbance is 450 nm among at least one of the two or more maximum absorption wavelengths at the time of color development. That is all you need.
  • the maximum absorption wavelength is measured by measuring a transmission spectrum in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) at 25 ° C. in the atmosphere of air, and measuring the light intensity.
  • UV3100 manufactured by Shimadzu Corporation
  • the wavelength at which is minimized shall be measured.
  • Examples of the dye that develops and decolors upon exposure include leuco compounds.
  • Examples of the dye that can be erased by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, anthraquinone dyes, and the like.
  • a leuco compound is preferable from the viewpoint of visibility.
  • the leuco compound examples include triarylmethane-based (for example, triphenylmethane-based), spiropyran-based, fluoran-based, diarylmethane-based, rhodamine lactam-based, indolylphthalide-based, and leucooramine-based leuco compounds.
  • a leuco compound (triarylmethane dye) having a triarylmethane skeleton is preferable, and a triphenylmethane dye is more preferable.
  • the leuco compound preferably has a lactone ring, a sultin ring, or a sultone ring from the viewpoint of visibility.
  • the leuco compound When the leuco compound has a lactone ring, a sultin ring, or a sultone ring, it reacts with an acid generated from, for example, a photoacid generator to change to a ring-closed state and disappear, or to a ring-opened state. It can change and color.
  • a lactone ring, a sultin ring, or a sultone ring that is opened is preferable, and a leuco compound that has a sultone ring and that discolors when the sultone ring is closed is more preferable.
  • the dye is preferably a water-soluble compound for the purpose of preventing defects due to precipitation of the dye in the aqueous resist stripping solution. That the dye is water-soluble means that the amount of the dye dissolved in 100 parts by mass of water at 25 ° C. is 0.1 parts by mass or more (preferably 1 part by mass or more, more preferably 5 parts by mass or more). .
  • the dye is at least one selected from a dye represented by the following formula I, a ring-opened product of the dye represented by the following formula I, and a neutralized product of the ring-opened product. It is preferable to include.
  • Ar and Ar ′ each independently represents an aromatic group.
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a monovalent substituent.
  • the ring-closed body, ring-opened body, and neutralized body of the ring-opened body in the present disclosure will be described below using Compound A-1 described below as an example. The same applies to other compounds represented by formula (I).
  • the dye of the present disclosure exists in an equilibrium state of a ring-closed body, a ring-opened body, and a neutralized body of a ring-opened body in an intermediate layer, for example, as shown below. For example, if the pH in the intermediate layer is acidic, the abundance ratio of the ring-closed body increases, and the abundance ratio of the ring-opened body and the neutralized body of the ring-opening body relatively decreases.
  • the abundance ratio of the ring-opened product and the neutralized product of the ring-opened product increases, and the abundance ratio of the ring-closed product relatively decreases.
  • the ring-closed body, ring-opened body, and neutralized body of the ring-opened body have different colors at the time of color development, for example, when the intermediate layer contains a photoacid generator, it is included in the exposed intermediate layer. As a result of the release of the acid from the photoacid generator, the pH of the exposed portion is reduced, and the color of the coloring dye changes. On the other hand, there is no color change in the unexposed area. Thereby, good visibility of the exposed part and the unexposed part can be realized.
  • the component (G) that is a pH adjuster (such as NaOH) Is preferably used.
  • the aromatic group in Ar and Ar ′ in the formula (I) may be an aryl group or a heteroaryl group, and even if it is a monocyclic aromatic group, two or more rings are condensed. It may be a condensed ring.
  • Ar and Ar ′ in formula (I) may combine to form a ring.
  • Ar and Ar ′ are preferably a 5-membered ring or a 6-membered ring.
  • the aromatic group in Ar and Ar ′ in formula (I) may have a substituent.
  • Ar and Ar ′ may have a plurality of the above substituents.
  • substituents examples include a hydroxy 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 hydroxy group, a halogen group, and a dialkylamino group.
  • Alkylarylamino group and diarylamino group are preferable.
  • the substituent can be bonded to at least one of the ortho position, the meta position, and the para position. Among them, it is preferable to bond to at least one of the ortho position and the para position, and it is more preferable to bond to at least the para position.
  • the halogen atom is preferably a bromo atom (bromine atom) and an iodine atom, and more preferably a bromo atom (bromine atom).
  • 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 be further substituted with a substituent.
  • Ar and Ar ′ are preferably a phenyl group having a hydroxy group and a phenyl group substituted by a halogen atom.
  • the total carbon number of Ar and Ar ′ in the formula (I) is preferably 4 to 50, more preferably 6 to 40, and more preferably 10 to 30 from the viewpoints of sensitivity and visibility. More preferably.
  • R 1 , R 2 , R 3 and R 4 in formula (I) are each independently a hydrogen atom, hydroxy group, halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, dialkylamino group, alkylarylamino group And a diarylamino group. Of these, a hydrogen atom is preferable.
  • the dye may be used alone or in combination of two or more.
  • the content of the dye in the photosensitive transfer material according to the present disclosure is preferably 0.01% by mass to 10% by mass with respect to the total solid content of the intermediate layer composition from the viewpoint of visibility. It is more preferably from 8% by mass to 8% by mass, and further preferably from 0.5% by mass to 5% by mass.
  • the “solid content” in the intermediate layer composition means a component excluding a volatile component (for example, a solvent).
  • the content of the dye means the content of the dye when all of the dyes included in the intermediate layer composition are in a colored state.
  • the absorbance is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) at 25 ° C. in an air atmosphere to prepare a calibration curve.
  • the amount of the dye contained in the intermediate layer composition is calculated from the calibration curve prepared from the absorbance of the dye and the absorbance of the intermediate layer composition.
  • the intermediate layer can include a polymer.
  • the polymer used for the intermediate layer is preferably a water-soluble resin.
  • water-soluble resins 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. These resins are mentioned. Of these, cellulose-based resins are preferable, and hydroxypropylcellulose and hydroxypropylmethylcellulose are more preferable.
  • the water solubility of the polymer in the present disclosure means that the amount of the polymer dissolved in 100 parts by mass of water at 25 ° C. is 0.1 parts by mass or more (preferably 1 part by mass or more, more preferably 5 parts by mass or more). It means that there is.
  • the content of the polymer in the photosensitive transfer material according to the present disclosure is preferably 20% by mass to 100% by mass, and preferably 50% by mass to the total solid content of the intermediate layer composition from the viewpoint of adhesion. More preferably, it is 100 mass%.
  • the intermediate layer preferably contains a surfactant from the viewpoint of film thickness uniformity.
  • a surfactant any of anionic, cationic, nonionic (nonionic), or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. Examples of nonionic surfactants are those described above.
  • the intermediate layer can contain an inorganic filler.
  • the inorganic filler in the present disclosure is not particularly limited. Silica particles, aluminum oxide particles, zirconium oxide particles and the like can be mentioned, and silica particles are more preferable. From the viewpoint of transparency, particles having a small particle diameter are preferable, and those having an average particle diameter of 100 nm or less are more preferable. For example, if it is a commercial product, Snowtex (registered trademark) is preferably used.
  • volume fraction of the inorganic filler in the photosensitive transfer material according to the present disclosure is based on the total solid content of the intermediate layer composition from the viewpoint of adhesion between the intermediate layer and the photosensitive layer.
  • the content is preferably 10% by mass to 80% by mass, and more preferably 20% by mass to 60% by mass.
  • the intermediate layer can contain a pH adjusting agent.
  • the pH adjusting agent By including the pH adjusting agent, the coloring state or decoloring state of the dye in the composition can be more stably maintained, and the adhesion to the substrate is further improved.
  • Sodium hydroxide is preferred from the viewpoint of water solubility. From the viewpoint of adhesion between the resist layer and the intermediate layer, an organic ammonium salt is preferable.
  • organic ammonium salts include primary ammonium salts, secondary ammonium salts, tertiary ammonium salts, and quaternary ammonium salts, with quaternary ammonium salts being preferred.
  • examples of the quaternary ammonium salt include tetraalkylammonium hydroxide which may have a substituent.
  • tetramethylammonium hydroxide triethylmethylammonium hydroxide, tetraethylammonium hydroxide, tetra
  • examples thereof include propylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, hexadecyltrimethylammonium hydroxide, choline, benzyltrimethylammonium, benzyltriethylammonium, tris (2-hydroxyethyl) methylammonium hydroxide.
  • 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
  • substituents include an aryl group having 6 to 12 carbon atoms (for example, a phenyl group) and a hydroxy group.
  • the content of the pH adjusting agent in the photosensitive transfer material according to the present disclosure is 1% by mass to 50% by mass with respect to the total solid content of the intermediate layer composition from the viewpoint of stabilizing the coloring or decoloring state of the dye. %, Preferably 3% by mass to 30% by mass.
  • the intermediate layer can contain a photoacid generator.
  • the photoacid generator is not particularly limited. They may be the same as the photoacid generator described below.
  • the photoacid generator can be included in the intermediate layer composition and applied in advance. However, when the resist layer composition is applied, the photoacid generator diffuses and can be included in the intermediate layer.
  • the photosensitive transfer material in the present disclosure is a negative photosensitive transfer material
  • the photosensitive transfer material can contain a photoradical generator.
  • Examples of the photo radical generator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p′-dimethoxybenzyl), TAZ-110 (trade name: Midori) Chemical Co., Ltd.), benzophenone, TAZ-111 (trade name: Midori Chemical Co., Ltd.), Irgacure OXE01, OXE02, OXE03 (BASF), Omnirad 651 and 369 (trade names: IGM Resins BV) Examples include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.). Moreover, the photoinitiator mentioned later can also be used as a photoradical generator.
  • DBE ethyl dimethylaminobenzoate
  • anisyl p,
  • the photosensitive transfer material in the present disclosure is a negative photosensitive transfer material
  • the photosensitive transfer material can contain a photobase generator.
  • photobase generators examples include 2-nitrobenzylcyclohexyl carbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaamminecobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6 -Dimethyl-3, -Diacetyl-4- (2-nitrophenyl)
  • the average film thickness of the intermediate layer is preferably 0.3 ⁇ m to 10 ⁇ m, more preferably 0.3 ⁇ m to 5 ⁇ m, and more preferably 0.3 ⁇ m to 2 ⁇ m from the viewpoints of adhesion between the intermediate layer and the resist layer and pattern formability. Is particularly preferred.
  • the average value is preferably measured and calculated at 10 points or more. Specific examples include surface shape measurement and cross-sectional optical microscope or electron microscope observation. In addition, Bruker's Dektak series can be suitably used for surface shape measurement. Moreover, a scanning electron microscope (SEM) can be used suitably for cross-sectional observation. Moreover, it is preferable that the thickness of the said intermediate
  • the intermediate layer can have two or more layers.
  • the average film thickness of each layer is not particularly limited as long as it is within the above range.
  • the average of the layers closest to the resist layer The film thickness is preferably 0.3 ⁇ m to 10 ⁇ m, more preferably 0.3 ⁇ m to 5 ⁇ m, and particularly preferably 0.3 ⁇ m to 2.0 ⁇ m, from the viewpoints of adhesion between the intermediate layer and the resist layer and pattern formability. .
  • An intermediate layer composition for forming an intermediate layer by mixing each component and a solvent in a predetermined ratio at an arbitrary method, and dissolving by stirring can be prepared.
  • the composition prepared as described above can be used after being filtered using a filter having a pore size of 3.0 ⁇ m.
  • the intermediate layer can be formed on the temporary support by applying the intermediate layer composition to the temporary support and drying it.
  • the coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
  • the resist layer according to the present disclosure is a layer that 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. It is preferable that the said resist layer is a layer formed with the resist layer composition in this indication.
  • the resist layer in the present disclosure is preferably a chemically amplified positive resist layer from the viewpoint of high sensitivity.
  • the resist layer composition according to the present disclosure is also referred to as a polymer (also referred to as “specific polymer”) containing a structural unit having an acid group protected by an acid-decomposable group (also referred to as “structural unit b”). ) Can be contained.
  • the resist layer composition according to the present disclosure may contain another polymer.
  • the specific polymer having the structural unit b and other polymers are also collectively referred to as “polymer component”.
  • the structural unit b having an acid-decomposable and protected acid group in the specific polymer undergoes a deprotection reaction to be an acid group by the action of a catalytic amount of an acidic substance generated by exposure.
  • This acid group enables dissolution by development.
  • 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.
  • the resist layer composition is a polymer having a structural unit b1 represented by the following formula II as the structural unit b as a polymer component from the viewpoint of pattern formability, solubility in a developer, and transferability.
  • the polymer component preferably includes a specific polymer having the structural unit b1 represented by the following formula II as the structural unit b and having a glass transition temperature of 90 ° C. or less.
  • a specific polymer having a structural unit b1 represented by the following 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 ° C. or lower is included. More preferably.
  • the specific polymer contained in the resist layer composition may be one type or two or more types.
  • the polymer component includes a polymer having at least a structural unit b having a group in which an acid group is protected with an acid-decomposable group.
  • an extremely sensitive chemically amplified positive resist layer composition can be obtained.
  • the “acid group protected with an acid-decomposable group” in the present disclosure can be any known acid-decomposable group, and is not particularly limited.
  • the acid-decomposable group examples include groups that are 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 protected with a group represented by the formula II described later). Group) or a group that is relatively difficult to be decomposed by an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).
  • the acid-decomposable group is preferably a group having a structure protected in the form of an acetal.
  • the structural unit b having a group in which the acid group is protected with an acid-decomposable group is preferably a structural unit b1 represented by the following formula II from the viewpoint of sensitivity and resolution.
  • R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R 1 and R 2 is an alkyl group or an aryl group, and R 3 is an alkyl group Or an aryl group, R 1 or R 2 and R 3 may be linked to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group.
  • R 1 or R 2 when R 1 or R 2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R 1 or R 2 is an aryl group, a phenyl group is preferred. R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Further, the alkyl group and aryl group in R 1 to R 3 may have a substituent.
  • R 1 or R 2 and R 3 may be linked to form a cyclic ether, and R 1 or R 2 and R 3 are preferably linked to form a cyclic ether.
  • the number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
  • X represents a single bond or an arylene group, and a single bond is preferable.
  • the arylene group may have a substituent.
  • R 4 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the glass transition temperature (Tg) of the specific polymer can be further lowered. More specifically, the structural unit in which R 4 in Formula II is a hydrogen atom is preferably 20% by mass or more with respect to the total amount of the structural unit b1 contained in the specific polymer.
  • the content (content ratio: mass ratio) of the structural unit in which R 4 in formula II is a hydrogen atom in the structural unit b1 is calculated by a conventional method from 13 C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of the peak intensity.
  • the structural unit represented by the following formula b2 is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.
  • R 34 represents a hydrogen atom or a methyl group
  • R 35 to R 41 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 34 is preferably a hydrogen atom.
  • R 35 to R 41 are preferably hydrogen atoms.
  • R 34 represents a hydrogen atom or a methyl group.
  • the structural unit b is preferably a structural unit b3 represented by the following formula b3 from the viewpoint of suppressing deformation of the pattern shape.
  • R B1 and R B2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R B1 and R B2 is an alkyl group or an aryl group, and R B3 is an alkyl group or Represents an aryl group, R B1 or R B2 and R B3 may be linked to form a cyclic ether, R B4 represents a hydrogen atom or a methyl group, and X B represents a single bond or a divalent linking group; R B12 represents a substituent, and n represents an integer of 0 to 4.
  • R B1 or R B2 when R B1 or R B2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R B1 or R B2 is an aryl group, a phenyl group is preferable.
  • R B1 and R B2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R B3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group and aryl group in R B1 to R B3 may have a substituent.
  • R B1 or R B2 and R B3 may be linked to form a cyclic ether, and R B1 or R B2 and R B3 are preferably linked to form a cyclic ether.
  • the number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
  • X B represents a single bond or a divalent linking group, and represents a single bond or an alkylene group, —C ( ⁇ O) O—, —C ( ⁇ O) NR N —, —O—, or a combination thereof.
  • the alkylene group may be linear, branched or cyclic, and may have a substituent.
  • the alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • X B contains —C ( ⁇ O) O—
  • an embodiment in which the carbon atom contained in —C ( ⁇ O) O— and the carbon atom bonded to R B4 are directly bonded is preferable.
  • R N represents an alkyl group or a hydrogen atom, preferably an alkyl group or a hydrogen atom having 1 to 4 carbon atoms, more preferably a hydrogen atom.
  • R B12 represents a substituent, and is preferably an alkyl group or a halogen atom.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
  • R B4 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of lowering the Tg of the specific polymer. More specifically, the structural unit in which R B4 in formula b3 is a hydrogen atom is preferably 20% by mass or more with respect to the total content of structural unit b contained in the specific polymer. Incidentally, in the structural unit b, the content of the structural unit R B4 is a hydrogen atom in the formula b3 (content: weight ratio) is calculated by the usual method from the 13 C- nuclear magnetic resonance spectra (NMR) measurements It can be confirmed by the intensity ratio of the peak intensity.
  • NMR 13 C- nuclear magnetic resonance spectra
  • the structural unit represented by the following formula b4 is more preferable from the viewpoint of suppressing deformation of the pattern shape.
  • R B4 represents a hydrogen atom or a methyl group
  • R B5 to R B11 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R B12 represents a substituent
  • n is 0
  • R B4 is preferably a hydrogen atom.
  • R B5 to R B11 are preferably hydrogen atoms.
  • R B12 represents a substituent, and is preferably an alkyl group or a halogen atom.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
  • R B4 represents a hydrogen atom or a methyl group.
  • the structural unit b contained in the specific polymer may be one type or two or more types.
  • 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 more preferably 30% by mass to 30% by mass with respect to the total mass of the specific polymer. More preferably, it is 70 mass%.
  • the content (content ratio: mass ratio) of the structural unit b in the specific polymer can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from 13 C-NMR measurement.
  • the proportion of the structural unit b is preferably 5% by mass to 80% by mass with respect to the total mass of the polymer component, It is more preferably 10% by mass to 80% by mass, particularly preferably 10% by mass to 40% by mass, and most preferably 10% by mass to 30% by mass.
  • the specific polymer preferably includes a structural unit bb having an acid group.
  • the structural unit bb is a structural unit including a protecting group, for example, an acid group that is not protected by an acid-decomposable group, that is, an acid group that does not have a protecting group.
  • the structural unit containing an acid group which is the structural unit bb, is a structural unit derived from styrene or a structural unit derived from a vinyl compound by an acid group, or a structure derived from (meth) acrylic acid. More preferably it is a unit.
  • the structural unit bb contained in the specific polymer may be only one type or two or more types.
  • the specific polymer preferably contains 0.1% by mass to 20% by mass, and 0.5% by mass to 15% by mass of the structural unit having an acid group (the structural unit bb) with respect to the total mass of the specific polymer.
  • the content is more preferably 1% by mass to 10% by mass. When it is in the above range, the pattern formability becomes better.
  • the content (content ratio: mass ratio) of the structural unit b in the specific polymer can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from 13 C-NMR measurement.
  • the specific polymer does not impair the effects of the photosensitive transfer material according to an embodiment of the present invention, except for the structural unit b and the structural unit bb described above, other structural units (hereinafter sometimes referred to as the structural unit bbb). It may be included in the range.
  • the monomer for forming the structural unit bbb is not particularly limited, and examples thereof include styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, and unsaturated dicarboxylic acid diesters.
  • Bicyclounsaturated compounds maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, groups having an aliphatic cyclic skeleton, other Mention may be made of saturated compounds.
  • Various characteristics of the specific polymer can be adjusted by adjusting at least one of the kind and the content using the structural unit bbb. In particular, the Tg of the specific polymer can be easily adjusted to 90 ° C. or less by appropriately using the structural unit bbb.
  • the specific polymer may contain only one type of structural unit bbb or may contain two or more types.
  • the structural unit bbb specifically includes styrene, tert-butoxystyrene, methylstyrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, (meth) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) Mention may be made of structural units formed by polymerizing benzyl acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate, or the like. In addition, the compounds described in paragraphs 00
  • a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton is preferable from the viewpoint of improving the electrical characteristics of the resulting photosensitive transfer material.
  • monomers that form these structural units include styrene, tert-butoxystyrene, methylstyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, And benzyl (meth) acrylate etc. are mentioned.
  • a structural unit derived from cyclohexyl (meth) acrylate is preferably exemplified.
  • (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion.
  • (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion.
  • Specific examples 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 still more preferably 50% by mass or less with respect to the total mass of the specific polymer.
  • the lower limit may be 0% by mass, but is preferably 1% by mass or more, and more preferably 5% by mass or more. Within the above range, the resolution and the adhesion of the resist layer formed by the resist layer composition are further improved.
  • the specific polymer includes, as the structural unit bbb, a structural unit having an acid group ester in the structural unit bb from the viewpoint of optimizing the solubility in the developer and the physical properties of the resist layer described later.
  • the specific polymer preferably includes a structural unit having an acid group as the structural unit bb, and further includes a structural unit bbb including a carboxylic acid ester group as a copolymerization component, for example, derived from (meth) acrylic acid.
  • a polymer containing the structural unit bb and a structural unit derived from cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate is more preferred.
  • this indication is not limited to the following illustrations.
  • the ratio of the structural unit and the weight average molecular weight in the following exemplary compounds are appropriately selected in order to obtain preferable physical properties.
  • the glass transition temperature (Tg) of the specific polymer in the present disclosure is preferably 90 ° C. or less.
  • Tg is 90 ° C. or lower, the resist layer formed from the resist layer composition has high adhesion and is excellent in transferability.
  • the Tg is more preferably 60 ° C. or less, and further preferably 40 ° C. or less.
  • the lower limit of Tg is not particularly limited, but is preferably ⁇ 20 ° C. or higher, and more preferably ⁇ 10 ° C. or higher. When the Tg of the specific polymer is ⁇ 20 ° C.
  • the glass transition temperature (Tg) of the entire polymer component in the present disclosure is preferably 90 ° C. or lower, more preferably 60 ° C. or lower, and 40 ° C. or lower from the viewpoint of transferability. Is more preferable.
  • the glass transition temperature of a specific polymer can be measured using differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the specific measuring method was performed in accordance with the method described in JIS K 7121 (1987) or JIS K 6240 (2011).
  • the glass transition temperature in the present disclosure uses an extrapolated glass transition start temperature (hereinafter sometimes referred to as Tig).
  • Tig extrapolated glass transition start temperature
  • the method for measuring the glass transition temperature will be described more specifically.
  • the heating rate is about 20 ° C./min and about 30 times higher than the temperature at which the glass transition is completed. Heat to a higher temperature and draw a DTA or DSC curve.
  • the extrapolated glass transition start temperature (Tig) that is, the glass transition temperature Tg in the present disclosure, is a straight line obtained by extending the base line on the low temperature side to the high temperature side in the DTA curve or DSC curve, and the curve of the step-like change portion of the glass transition. The temperature at the point of intersection with the tangent drawn at the point where the slope of the maximum is.
  • the FOX formula is used as a guideline.
  • the FOX formula is used as a guideline.
  • Tg of the homopolymer of the first structural unit contained in the polymer component is Tg1
  • W1 is the mass fraction of the copolymer of the first structural unit
  • a copolymer having a desired Tg can be obtained by adjusting the type and mass fraction of each constituent unit contained in the copolymer using the FOX formula described above. It is also possible to adjust the Tg of the polymer by adjusting the weight average molecular weight of the polymer.
  • 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, the melt viscosity of the resist layer in the photosensitive transfer material described later is kept low, and bonding at a low temperature (for example, 130 ° C. or less) is performed when bonding to the 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 further preferably 10,000 to 30,000. preferable.
  • the weight average molecular weight of the specific polymer can be measured by GPC (gel permeation chromatography), and various commercially available devices can be used as the measuring device. It is known to those skilled in the art.
  • GPC gel permeation chromatography
  • HLC registered trademark
  • -8220GPC manufactured by Tosoh Corp.
  • TSKgel registered trademark
  • Super HZM-M 4 .6 mm ID ⁇ 15 cm, manufactured by Tosoh Corp.
  • Super HZ4000 4 mm ID ⁇ 15 cm, manufactured by Tosoh Corp.
  • Super HZ3000 4.6 mm ID ⁇ 15 cm, manufactured by Tosoh Corp.
  • Super HZ2000 4.6 mm ID) ⁇ 15 cm, manufactured by Tosoh Corporation
  • THF tetrahydrofuran
  • the measurement conditions are 0.2 mass%, the flow rate is 0.35 ml / min, the sample injection amount is 10 ⁇ l, the measurement temperature is 40 ° C., and a differential refractive index (RI) detector is used. be able to.
  • the calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “ It can be produced using any of the seven samples of “A-2500” and “A-1000”.
  • the ratio (dispersion degree) between the number average molecular weight and the weight average molecular weight of the specific polymer is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.
  • the production method (synthesis method) of the specific polymer is not particularly limited.
  • a polymerizable monomer for forming the structural unit b1 represented by the formula II and a structural unit bb having an acid group are formed. It can synthesize
  • the resist layer composition according to the present disclosure preferably contains the specific polymer in a proportion of 50% by mass to 99.9% by mass with respect to the total solid content of the resist layer composition from the viewpoint of sensitivity and resolution. More preferably, it is contained in a proportion of 70 mass% to 98 mass%.
  • the resist layer composition includes, as a polymer component, a polymer that does not include the structural unit b (in addition to the specific polymer, in a range that does not impair the effect of the resist layer composition according to the present disclosure (“other polymer”). May be included).
  • the blending amount of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less in the total polymer component, More preferably, it is 20 mass% or less.
  • all the polymers contained in the said polymer component are polymers which have at least the structural unit which has the acid group mentioned above, respectively.
  • the compound applicable to the plasticizer mentioned later, a heterocyclic compound, and surfactant shall not be contained in the said polymer component.
  • the resist layer composition may contain only one type of other polymer, or may contain two or more types.
  • polyhydroxystyrene can be used, which are commercially available, such as SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer).
  • ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncryl 690, Joncryl 6 Joncryl 67, Joncryl 586 (manufactured by BASF) or the like can also be used.
  • the resist layer composition according to the present disclosure preferably contains a photoacid generator.
  • the photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiation with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
  • the photoacid generator used in the present disclosure is preferably a compound that generates an acid in response to an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but its chemical structure is not limited.
  • a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
  • the pKa of the acid generated from the photoacid generator used in the present disclosure is preferably 4.0 or less, more preferably 3.0 or less, from the viewpoint of sensitivity and visibility.
  • the lower limit of the pKa of the acid generated from the photoacid generator is not particularly defined, but is preferably, for example, -10.0 or more, and more preferably -4.0 or more from the viewpoint of sensitivity and visibility.
  • -3.5 or more is more preferable, and -3.0 or more is particularly preferable.
  • the acid generated from the photoacid generator is preferably at least one acid selected from the group consisting of phosphoric acid and sulfonic acid from the viewpoint of sensitivity and visibility, and more preferably sulfonic acid.
  • it is a sulfonic acid represented by the following formula C1 or C2.
  • R S represents an alkyl group
  • L S represents an alkylene group having 2 or more carbon atoms
  • ns represents 0 or 1
  • R S is an alkyl group having a halogen atom.
  • n is 1
  • each X S independently represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group
  • ms represents an integer of 0 to 5.
  • the alkyl group in R S may have a substituent.
  • substituents include a halogen atom, an aryl group, an alkoxy group, and an aryloxy group.
  • the number of carbon atoms of the alkyl group in R S is preferably 1-20, and more preferably 2-16.
  • L S is preferably 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 S each independently 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 a methyl group. Is particularly preferred.
  • ms is preferably an integer of 0 to 3, more preferably 0 or 1, and particularly preferably 1.
  • the photoacid generator examples include an ionic photoacid generator and a nonionic photoacid generator.
  • the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound described later from the viewpoint of sensitivity and resolution, and an oxime sulfonate compound. It is more preferable to contain.
  • nonionic photoacid generators examples include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
  • the photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion.
  • These photoacid generators can be used singly or in combination of two or more.
  • Specific examples of trichloromethyl-s-triazines and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP 2011-212494A.
  • oxime sulfonate compound that is, a compound having an oxime sulfonate structure
  • a compound having an oxime sulfonate structure represented by the following formula C3 is preferable.
  • R 21 represents an alkyl group or an aryl group
  • * represents a bonding site with another atom or another group.
  • any group may be substituted, and the alkyl group in R 21 may be linear or branched, or may have a ring structure. You may have. Acceptable substituents are described below.
  • the alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • the alkyl group of R 21 is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or other bridged alicyclic group) , Preferably a bicycloalkyl group or the like) or a halogen atom.
  • a aryl group for R 21 an aryl group having 6 to 18 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable.
  • the aryl group of R 21 may be substituted with one or more groups 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 also preferably an oxime sulfonate compound described in paragraphs 0078 to 0111 of JP 2014-85643 A. Examples thereof include compounds described in paragraphs 0080 to 0081 of JP-A No. 2015-151347.
  • Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, quaternary ammonium salts, and the like. Of these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.
  • ionic photoacid generators described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.
  • a photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
  • the content of the photoacid generator in the resist layer composition is preferably 0.1% by mass to 15% by mass with respect to the total solid content of the resist layer composition from the viewpoint of sensitivity and resolution. More preferably, it is 0.5 to 10% by mass.
  • the resist layer composition preferably contains a polymerizable compound.
  • a polymerizable compound an ethylenically unsaturated compound is preferable.
  • the ethylenically unsaturated compound is a component that contributes to the photosensitivity (that is, photocurability) of the photosensitive transfer material and the strength of the cured film.
  • An ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups.
  • the resist layer composition preferably includes a bifunctional or higher functional ethylenically unsaturated compound as the ethylenically unsaturated compound.
  • the bifunctional or higher functional ethylenically unsaturated compound means a compound having two or more ethylenically unsaturated groups in one molecule.
  • a (meth) acryloyl group is more preferable.
  • a (meth) acrylate compound is preferable.
  • bifunctional ethylenically unsaturated compound there is no restriction
  • the bifunctional ethylenically unsaturated compound include tricyclodecane dimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,6-hexane. Examples include diol di (meth) acrylate.
  • bifunctional ethylenically unsaturated compound examples include tricyclodecane dimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, Shin-Nakamura Chemical Co., Ltd.).
  • A-DCP tricyclodecane dimethanol diacrylate
  • DCP Shin-Nakamura Chemical Co., Ltd.
  • DCP Shin-Nakamura Chemical Co., Ltd.
  • 1,9-nonanediol diacrylate A-NOD-N, Shin-Nakamura Chemical Co., Ltd.
  • 1,6-hexanediol diacrylate A-HD-N, Shin
  • bifunctional ethylenically unsaturated compound a bifunctional ethylenically unsaturated compound having a bisphenol structure is also preferably used.
  • the bifunctional ethylenically unsaturated compound having a bisphenol structure include the compounds described in paragraphs 0072 to 0080 of JP-A-2016-224162. Specific examples include alkylene oxide-modified bisphenol A di (meth) acrylate, and 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane, 2,2-bis (4- (methacryloxyethoxy). Propoxy) phenyl) propane and the like are preferred.
  • the trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds.
  • Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth).
  • Examples include acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and (meth) acrylate compounds having a glycerin tri (meth) acrylate skeleton.
  • (tri / tetra / penta / hexa) (meth) acrylate is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate.
  • (Tri / tetra) (meth) acrylate” is a concept including tri (meth) acrylate and tetra (meth) acrylate.
  • Examples of the ethylenically unsaturated compound include a caprolactone-modified compound of (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), Alkylene oxide modified compound of (meth) acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., Ltd. Etc.), and ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • KAYARAD registered trademark
  • DPCA-20 Alkylene oxide modified compound of (meth) acrylate compound
  • ATM-35E Alkylene oxide modified compound of (meth)
  • Examples of the ethylenically unsaturated compound include urethane (meth) acrylate compounds (preferably trifunctional or higher functional urethane (meth) acrylate compounds).
  • Examples of the tri- or higher functional urethane (meth) acrylate compound include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (Shin-Nakamura Chemical Industry ( Etc.).
  • an ethylenically unsaturated compound contains the ethylenically unsaturated compound which has an acid group from a viewpoint of developability improvement.
  • the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxy group, and a carboxy group is preferable.
  • PETA pentaerythritol tri- and tetraacrylate
  • DPHA dipentaerythritol penta and hexaacrylate
  • the ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group and a carboxylic acid anhydride thereof.
  • the bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group is not particularly limited and can be appropriately selected from known compounds.
  • Examples of the bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.), or Aronix M-510 (manufactured by Toagosei Co., Ltd.) can be preferably used.
  • the ethylenically unsaturated compound having an acid group is also preferably a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A No. 2004-239942.
  • the contents of this publication are incorporated into this disclosure.
  • the weight average molecular weight (Mw) of the polymerizable compound used in the present disclosure is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and more preferably 300 to 2,200. Particularly preferred.
  • the ratio of the content of the polymerizable compound having a molecular weight of 300 or less among the polymerizable compounds used in the resist layer composition is based on all the ethylenically unsaturated compounds contained in the resist layer composition. 30 mass% or less is preferable, 25 mass% or less is more preferable, and 20 mass% or less is still more preferable.
  • a polymeric compound may be used individually by 1 type, or may use 2 or more types together.
  • the content of the polymerizable compound in the resist layer composition is preferably 1% by weight to 70% by weight, more preferably 10% by weight to 70% by weight, and more preferably 20% by weight to the total weight of the resist layer composition. 60% by mass is more preferable, and 20% by mass to 50% by mass is particularly preferable.
  • the content of the bifunctional ethylenically unsaturated compound is determined by the resist layer composition. Is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 85% by mass, and still more preferably 30% by mass to 80% by mass with respect to all the ethylenically unsaturated compounds contained in.
  • the content of the trifunctional or higher functional ethylenically unsaturated compound is preferably 10% by mass to 90% by mass, and 15% by mass with respect to all the ethylenically unsaturated compounds contained in the resist layer composition.
  • the content of the bifunctional or higher ethylenically unsaturated compound is 40% by mass or more and 100% with respect to the total content of the bifunctional ethylenically unsaturated compound and the trifunctional or higher ethylenically unsaturated compound. It is preferably less than mass%, more preferably 40 mass% to 90 mass%, further preferably 50 mass% to 80 mass%, and particularly preferably 50 mass% to 70 mass%. .
  • the resist layer composition may further contain a monofunctional ethylenically unsaturated compound.
  • the bifunctional or higher functional ethylenically unsaturated compound is a main component in the ethylenically unsaturated compound contained in the resist layer composition. It is preferable that Specifically, when the resist layer composition contains a bifunctional or higher functional ethylenically unsaturated compound, the content of the bifunctional or higher functional ethylenically unsaturated compound is the ethylene contained in the resist layer composition. 60% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass with respect to the total content of the unsaturated unsaturated compounds.
  • the resist layer composition contains an ethylenically unsaturated compound having an acid group (preferably a bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group or a carboxylic acid anhydride thereof), an acid group
  • an acid group preferably a bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group or a carboxylic acid anhydride thereof
  • an acid group preferably 1 to 50% by weight, preferably 1% to 20% by weight, more preferably 1% to 10% by weight, based on the resist layer composition. preferable.
  • the resist layer composition preferably contains a binder polymer having an acid group.
  • a binder polymer having an acid group an alkali-soluble resin is preferable.
  • the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group. Of these, a carboxy group is preferred as the acid group.
  • the acid value of the binder polymer having an acid group is not particularly limited, but from the viewpoint of alkali developability, an acid-soluble resin having an acid value of 60 mgKOH / g or more is preferable, and a carboxy group having an acid value of 60 mgKOH / g or more. It is especially preferable that it is a containing acrylic resin.
  • the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more (hereinafter sometimes referred to as the specific polymer A) is not particularly limited as long as the above acid value is satisfied, and is appropriately selected from known resins. Can be used.
  • an alkali-soluble resin which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, paragraphs 0033 to 0052 of JP2010-237589A.
  • a containing acrylic resin or the like can be preferably used as the specific polymer A in the present disclosure.
  • the (meth) acrylic resin refers to a resin including at least one of a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid ester.
  • a preferable range of the copolymerization ratio of the monomer having a carboxy group in the specific polymer A is 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and more preferably 100% by mass of the polymer. Preferably, it is in the range of 12% by mass to 30% by mass.
  • the specific polymer A may have a reactive group, and means for introducing the reactive group into the specific polymer A include a hydroxyl group, a carboxy group, a primary, secondary amino group, an acetoacetyl group, and a sulfonic acid.
  • Examples 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, and the like.
  • the specific polymer A the following compound A is preferable.
  • the content ratio of each structural unit shown below can be changed as appropriate according to the purpose.
  • the acid value of the binder polymer having an acid group used in the present disclosure is preferably 60 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 150 mgKOH / g, from the viewpoint of alkali developability. More preferably, it is 60 mgKOH / g to 110 mgKOH / g.
  • the acid value means 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 10,000 or more, and further preferably 20,000 to 100,000.
  • any film-forming resin can be appropriately selected and used depending on the purpose.
  • polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin and the like can be preferably exemplified.
  • the binder polymer having an acid group may be used alone or in combination of two or more.
  • 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, and 20% by mass with respect to the total mass of the resist layer composition, from the viewpoint of photosensitivity. % To 80% by mass, more preferably 30% to 70% by mass.
  • the resist layer composition preferably includes a photopolymerization initiator.
  • the photopolymerization initiator receives actinic rays such as ultraviolet rays and visible rays, and initiates polymerization of the polymerizable compound (ethylenically unsaturated compound).
  • actinic rays such as ultraviolet rays and visible rays
  • a well-known photoinitiator can be used.
  • the photopolymerization initiator examples include a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as “oxime-based photopolymerization initiator”) and a photopolymerization initiator having an ⁇ -aminoalkylphenone structure (hereinafter referred to as “ ⁇ - An aminoalkylphenone photopolymerization initiator ”), a photopolymerization initiator having an ⁇ -hydroxyalkylphenone structure (hereinafter also referred to as“ ⁇ -hydroxyalkylphenone polymerization initiator ”), an acylphosphine oxide structure.
  • oxime-based photopolymerization initiator a photopolymerization initiator having an oxime ester structure
  • ⁇ - An aminoalkylphenone photopolymerization initiator a photopolymerization initiator having an ⁇ -aminoalkylphenone structure
  • ⁇ - An aminoalkylphenone photopolymerization initiator a
  • N-phenylglycine photopolymerization initiator photopolymerization initiator having an N-phenylglycine structure
  • N-phenylglycine photopolymerization initiator photopolymerization initiator having an N-phenylglycine structure
  • the photopolymerization initiator is at least selected from the group consisting of an oxime photopolymerization initiator, an ⁇ -aminoalkylphenone photopolymerization initiator, an ⁇ -hydroxyalkylphenone polymerization initiator, and an N-phenylglycine photopolymerization initiator.
  • 1 type is preferably included, and more preferably at least one selected from the group consisting of an oxime photopolymerization initiator, an ⁇ -aminoalkylphenone photopolymerization initiator, and an N-phenylglycine photopolymerization initiator. .
  • the photopolymerization initiator preferably includes at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and derivatives thereof.
  • the 2,4,5-triarylimidazole dimer and its derivative may be a compound represented by the following formula PI.
  • X 1 and X 2 are a chlorine atom.
  • the number of substituents is preferably 1 to 5, more preferably 1 to 3, and preferably 1. Is more preferable.
  • the substitution position is not particularly limited, and is preferably the ortho position or the para position. p and q are each independently an integer of 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-di (methoxyphenyl) imidazole dimer. 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4 , 5-diphenylimidazole dimer.
  • the substituents of the aryl groups of two 2,4,5-triarylimidazoles may be the same to give the target compound, or differently give an asymmetric compound.
  • photopolymerization initiator for example, polymerization initiators described in paragraphs 0031 to 0042 of JP2011-95716A and paragraphs 0064 to 0081 of JP2015-014783A may be used.
  • photopolymerization initiators include 1- [4- (phenylthio)]-1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, BASF Corporation 1)-[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF) 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379EG, manufactured by BASF), 2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE 907, manufactured by BASF), 2 Hydroxy-1- ⁇ 4- [4- (2-hydroxy) [
  • a photoinitiator may be used individually by 1 type, or may use 2 or more types together. Although there is no restriction
  • the resist layer composition may contain at least one polymerization inhibitor.
  • the polymerization inhibitor for example, a thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784 can be used. Among these, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.
  • the content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, and 0.01% by mass with respect to the total mass of the resist layer composition. % To 1% by mass is more preferable, and 0.01% to 0.8% by mass is even more preferable.
  • the resist layer composition according to the present disclosure preferably contains a basic compound.
  • the basic compound can be arbitrarily selected from basic compounds used in 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 JP-A-2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated in the present disclosure.
  • aliphatic amine examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like.
  • examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
  • aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.
  • heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, cyclohexylmorpholinoethylthiourea (CMTU), 1,5-diazabicyclo [4.3.0] -5-nonene, and 1,8- Diazabishi (B) [5.3.0] -7-undecene
  • Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
  • Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
  • the said basic compound may be used individually by 1 type, or may use 2 or more types together.
  • the content of the basic compound is preferably 0.001% by mass to 5% by mass and more preferably 0.005% by mass to 3% by mass with respect to the total solid content of the resist layer composition. preferable.
  • the resist layer composition according to the present disclosure preferably further contains a solvent (S). Moreover, in order to easily form a resist layer, which will be described later, the resist layer composition once contains a solvent to adjust the viscosity of the resist layer composition, apply and dry the resist layer composition containing the solvent, A resist layer can be suitably formed.
  • a solvent used in the present disclosure, a known solvent can be used.
  • Solvents 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, acetic acid Propyl, isopropyl acetate, isobutyl acetate, butyl acetate, tert-butyl acetate Le, cyclopentyl methyl ether, diisopropyl ether, propylene glycol monoethyl
  • the solvent which can be used for this indication may be used individually by 1 type, and it is more preferable to use 2 types together.
  • two or more solvents for example, combined use of propylene glycol monoalkyl ether acetates and dialkyl ethers, combined use of diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetates A combination with the above is preferred.
  • the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof. Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C.
  • propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), and An example is propylene glycol methyl-n-propyl ether (boiling point 131 ° C.).
  • Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate.
  • the content of the solvent in applying the resist layer composition is preferably 50 parts by weight to 1,900 parts by weight, and 100 parts by weight to 900 parts by weight per 100 parts by weight of the total solid content in the resist layer composition. More preferably, it is a part.
  • 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 0.5% by mass or less with respect to the total mass of the resist layer. More preferably it is.
  • the resist layer composition according to the present disclosure may contain known additives as necessary in addition to the above-described components such as the specific polymer and the photoacid generator.
  • the resist layer composition according to the present disclosure may contain a plasticizer for the purpose of improving plasticity.
  • the plasticizer preferably has a weight average molecular weight smaller than that of the specific polymer.
  • the weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, and still more preferably 800 or more and less than 4,000 from the viewpoint of imparting plasticity.
  • 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, the plasticizer preferably has an alkyleneoxy group in the molecule.
  • the alkyleneoxy group contained in the plasticizer preferably has the following structure.
  • R represents an alkylene group having 2 to 8 carbon atoms
  • n represents an integer of 1 to 50
  • * represents a bonding site with another atom.
  • a chemically amplified positive resist layer obtained by mixing compound X, a specific polymer and a photoacid generator, even if it is a compound having an alkyleneoxy group having the above structure referred to as “compound X”.
  • compound X a compound having an alkyleneoxy group having the above structure
  • an optional surfactant is not used as a plasticizer in the present disclosure because it is generally not used in an amount that provides plasticity to the resist layer composition.
  • the content of the plasticizer is preferably 1% by mass to 50% by mass with respect to the total solid content of the resist layer composition from the viewpoint of adhesion of the resist layer formed by the resist layer composition. More preferably, the content is 2% by mass to 20% by mass.
  • the said resist layer composition may contain only 1 type of plasticizers, and may contain 2 or more types.
  • the resist layer composition according to the present disclosure may further include a sensitizer.
  • the sensitizer absorbs actinic rays and enters an electronically excited state.
  • the sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise
  • anthracene derivative a compound selected from the group consisting of an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a base styryl derivative, and a distyrylbenzene derivative is preferable, and an anthracene derivative is more preferable.
  • Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 1,10-dibromoanthracene, 2-ethylanthracene or 9,10-dimethoxyanthracene is preferred.
  • Examples of the sensitizer include compounds described in paragraphs 0139 to 0141 of International Publication No. 2015/092731.
  • the content of the sensitizer is preferably 0% by mass to 10% by mass and more preferably 0.1% by mass to 10% by mass with respect to the total solid content of the resist layer composition. .
  • the resist layer composition according to the present disclosure may include a heterocyclic compound.
  • a heterocyclic compound There is no restriction
  • heterocyclic monomers having d electrons such as silicon, sulfur, and phosphorus can be added.
  • the content of the heterocyclic compound in the resist layer composition is preferably 0.01% by mass to 50% by mass with respect to the total solid content of the resist layer composition.
  • the content is more preferably 0.1% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass. It is preferable in the said range from a viewpoint of adhesiveness and etching tolerance. Only 1 type may be used for a heterocyclic compound and it can also use 2 or more types together.
  • Specific examples of the compound having an epoxy group in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like.
  • a compound having an epoxy group in the molecule can be obtained as a commercial product.
  • JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Co., Ltd.), JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like, such as commercial products described in paragraph 0189 of JP2011-221494A can be mentioned.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and aliphatic epoxy resin is particularly preferable.
  • the compound containing an oxetanyl group is preferably used alone or mixed with a compound containing an epoxy group.
  • the heterocyclic compound is preferably a compound having an epoxy group from the viewpoint of etching resistance and line width stability of the resulting pattern.
  • the resist layer composition according to the present disclosure may contain an alkoxysilane compound.
  • Preferred examples of the alkoxysilane compound include trialkoxysilane compounds.
  • Examples of the alkoxysilane compound include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltriacoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, and ⁇ -methacryloxy.
  • ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, ⁇ -glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable.
  • the content of the alkoxysilane compound is preferably 0.1% by mass to 30% by mass and more preferably 0.5% by mass to 20% by mass with respect to the total solid content of the resist layer composition.
  • the resist layer composition according to the present disclosure preferably contains a surfactant from the viewpoint of film thickness uniformity.
  • a surfactant any of anionic, cationic, nonionic (nonionic), or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. .
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • F-Top manufactured by JEMCO
  • MegaFac manufactured by DIC Corporation
  • Florard Suditomo 3M
  • Surflon manufactured by Asahi Glass Co., Ltd.
  • PolyFox manufactured by OMNOVA
  • SH-8400 manufactured by Toray Dow Corning Co., Ltd.
  • a surfactant it contains a structural unit A and a structural unit B represented by the following formula I-1, and is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
  • a preferred example is a copolymer having (Mw) of 1,000 or more and 10,000 or less.
  • R 401 and R 403 each independently represent a hydrogen atom or a methyl group
  • R 402 represents a linear alkylene group having 1 to 4 carbon atoms
  • R 404 represents a hydrogen atom or a carbon group.
  • L represents an alkylene group having 3 to 6 carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p is a numerical value of 10 mass% to 80 mass%.
  • Q represents a numerical value of 20% to 90% by mass
  • r represents an integer of 1 to 18
  • s represents an integer of 1 to 10
  • * represents a bonding site with another structure. Represent.
  • L is preferably a branched alkylene group represented by the following formula (I-2).
  • R 405 in formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred.
  • the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
  • Surfactant may be used individually by 1 type and may use 2 or more types together.
  • the addition amount of the surfactant is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass with respect to the total solid content of the resist layer composition, and 0.01% More preferably, it is from 3% by mass to 3% by mass.
  • the resist layer composition according to the present disclosure includes metal oxide particles, an antioxidant, a dispersant, an acid multiplier, a development accelerator, a conductive fiber, a thermal radical polymerization initiator, a thermal acid generator, an ultraviolet absorber, Known additives such as thickeners and organic or inorganic suspending agents can be further added. Preferred embodiments of the other components are described in paragraphs 0165 to 0184 of JP 2014-85643 A, respectively, and the contents of this publication are incorporated in the present disclosure.
  • the said resist layer can contain preferably each component in the said resist layer composition other than the said solvent. Further, 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.
  • the thickness of the resist layer is preferably 0.5 ⁇ m to 20 ⁇ m. When the thickness of the resist layer is 20 ⁇ m or less, the resolution of the obtained pattern is good, and when it is 0.5 ⁇ m or more, it is preferable from the viewpoint of pattern linearity.
  • the thickness of the resist layer is more preferably 0.8 ⁇ m to 15 ⁇ m, and particularly preferably 1.0 ⁇ m to 10 ⁇ m.
  • a resist layer composition for forming a resist layer by mixing each component and a solvent in a predetermined ratio and by an arbitrary method, and dissolving by stirring.
  • a composition by preparing each solution of each component in advance in a solvent and then mixing the obtained solution at a predetermined ratio.
  • the composition prepared as described above can be used after being filtered using a filter having a pore size of 0.2 ⁇ m or the like.
  • the photosensitive transfer material according to the present disclosure 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 on which the intermediate layer is formed and drying.
  • the coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
  • the photosensitive transfer material according to the present disclosure has a temporary support.
  • the temporary support is a support that supports the intermediate layer and the resist layer and can be peeled off.
  • the temporary support used in the present disclosure preferably has light transmittance from the viewpoint that the intermediate layer and the resist layer can be exposed through the temporary support. Having light transmittance means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of light used for pattern exposure is a viewpoint of improving exposure sensitivity. Therefore, 60% or more is preferable, and 70% or more is more preferable.
  • Examples of the method for measuring the transmittance include a method of measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
  • Examples of the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is particularly preferable from the viewpoints of strength and flexibility.
  • 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 ⁇ m to 200 ⁇ m, and more preferably in the range of 10 ⁇ m to 150 ⁇ m from the viewpoint of ease of handling and versatility.
  • the thickness of the temporary support is selected according to the material from the viewpoints of strength as a support, flexibility required for bonding to a circuit wiring forming substrate, light transmittance required in the first exposure process, etc. do it.
  • a preferred embodiment of the temporary support is described, for example, in paragraphs 0017 to 0018 of JP 2014-85643 A, and the contents of this publication are incorporated in the present disclosure.
  • the photosensitive transfer material according to the present disclosure may have a layer other than the intermediate layer and the resist layer (hereinafter may be referred to as “other layer”).
  • other layers include a contrast enhancement layer, a cover film, and a thermoplastic resin layer.
  • the photosensitive transfer material according to the present disclosure has an intermediate layer and a resist layer in this order on a temporary support.
  • 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 are laminated in this order.
  • the intermediate layer 14-2 contains a pigment.
  • constituent materials and the like of the photosensitive transfer material according to the present disclosure will be described. Note that the above configuration in the present disclosure may be referred to as follows in the present disclosure.
  • a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group may be referred to as a “specific polymer”.
  • the resist layer When the resist layer is a positive resist layer, it may be referred to as a “positive resist layer”.
  • the first embodiment of the circuit wiring manufacturing method is as follows: A step of bonding the photosensitive transfer material according to the present disclosure to the substrate by bringing the resist layer of the photosensitive transfer material into contact with the substrate (bonding step); A step of exposing the intermediate layer and the resist layer of the photosensitive transfer material after the bonding step (exposure step); The resist layer after the pattern exposure process is developed to form a pattern (development process), and the process of etching the substrate in the region where the pattern is not disposed (etching process) is included in this order.
  • the substrate in the first embodiment of the circuit wiring manufacturing method may be a substrate in which a layer such as a desired conductive layer is provided on a base material such as glass, silicon, or a film. According to the first embodiment of the circuit wiring manufacturing method, a fine pattern can be formed on the substrate surface.
  • the second embodiment of the circuit wiring manufacturing method is And a plurality of conductive layers including a first conductive layer and a second conductive layer having different constituent materials from each other, and on the surface of the base material, in the order farthest from the surface of the base material, Bonding the resist layer of the photosensitive transfer material according to the present disclosure in contact with the first conductive layer to a substrate on which the first conductive layer and the second conductive layer which are layers are laminated Process, A first exposure step of pattern exposing the intermediate layer and the resist layer through the temporary support of the photosensitive transfer material after the bonding step; A first development step of developing the intermediate layer and the resist layer after the first exposure step to form a first pattern after peeling the temporary support from the intermediate layer and the resist layer after the first exposure step; A first etching step of etching at least the first conductive layer and the second conductive layer among the plurality of conductive layers in a region where the first pattern is not disposed; A second exposure step of pattern exposing the first pattern after the first etching step with a pattern
  • the third embodiment of the circuit wiring manufacturing method is a mode in which the first embodiment is repeated twice. That is, a step of bonding the resist layer of the photosensitive transfer material according to the present disclosure to the substrate in contact with the substrate (bonding step); A step of exposing the intermediate layer and the resist layer of the photosensitive transfer material after the bonding step (exposure step); Developing the resist layer after the pattern exposing step to form a pattern (developing step); A step of etching the substrate in the region where the pattern is not disposed (etching step); In this order, the resist layer of the photosensitive transfer material according to the present disclosure is bonded to the remaining resist layer after the etching step in contact with the remaining resist layer (bonding).
  • Combining step) and A step of exposing the intermediate layer and the resist layer of the photosensitive transfer material after the bonding step Exposure step); Developing the resist layer after the pattern exposing step to form a pattern (developing step); A step of etching the substrate in the region where the pattern is not disposed (etching step); Are included in this order.
  • the first and second photosensitive transfer materials may be the same or different.
  • the photosensitive transfer material used in the first bonding step is preferably a positive type, and the photosensitive transfer material used in the second bonding step may be a positive type or a negative type. Also good.
  • the third embodiment of the circuit wiring manufacturing method can be implemented by, for example, the following method.
  • An ITO film is formed on the base material by sputtering, and copper is formed thereon by a vacuum vapor deposition method to form a conductive pattern forming substrate.
  • a photosensitive transfer material is bonded onto the copper layer to form a laminate.
  • the laminated body is subjected to pattern exposure using a photomask provided with a pattern A having a configuration in which conductive layer pads are connected in one direction without peeling off the temporary support. Thereafter, the temporary support is peeled off, developed and washed with water to obtain a resin pattern drawn with pattern A.
  • the ITO layer is etched using an ITO etchant to obtain a substrate on which both copper and ITO are drawn in the pattern A.
  • a photosensitive transfer material is bonded onto the remaining resist layer.
  • pattern exposure is performed using a photomask provided with openings of pattern B in the aligned state, and the temporary support of the photosensitive transfer material is peeled off, followed by development and washing with water.
  • the copper wiring is etched, and the remaining resist layer is stripped using a stripping solution to obtain a circuit wiring board having a conductive pattern.
  • the circuit wiring manufacturing method according to the present disclosure can be used as a circuit wiring manufacturing method for a touch panel or a touch panel display device.
  • a touch panel or a touch panel display device can be used as a circuit wiring manufacturing method for a touch panel or a touch panel display device.
  • the substrate 22 has a plurality of conductive layers including the first conductive layer 24 and the second conductive layer 26 having different constituent materials, and the substrate 22 is formed on the surface of the substrate 22.
  • the photosensitive transfer material according to the present disclosure described above is applied to the substrate (circuit wiring forming substrate) 20 in which the first conductive layer 24 and the second conductive layer 26 which are the outermost surface layers are laminated in order from the surface of the substrate.
  • 100 resist layers 14-1 are brought into contact with the first conductive layer 24 and bonded together.
  • Such a bonding of the circuit wiring forming substrate and the photosensitive transfer material may be referred to as “transfer” or “laminate”.
  • the cover film 16 is provided on the positive resist layer 14 of the photosensitive transfer material 100 as shown in FIGS. 1 and 2, the cover film 16 is removed from the photosensitive transfer material 100 (positive resist layer 14). Thereafter, the resist layer 14-1 of the photosensitive transfer material 100 is brought into contact with the first conductive layer 24 and bonded thereto.
  • the bonding (transfer) of the photosensitive transfer material onto the first conductive layer is performed by stacking the resist layer side of the photosensitive transfer material on the first conductive layer, and applying pressure and heating with a roll or the like. Is preferred.
  • known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
  • the base material of the circuit wiring forming substrate is a resin film, roll-to-roll bonding can also be performed.
  • a base material is a glass base material or a film base material, and it is more preferable that it is a film base material.
  • the substrate is particularly preferably a sheet-shaped resin composition.
  • a base material is transparent.
  • transparent means that the transmittance in the visible light region of 400 nm to 800 nm is 90% or more.
  • the refractive index of the substrate is preferably 1.50 to 1.52.
  • the base material may be composed of a light-transmitting base material such as a glass base material, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used. Further, as the above-mentioned transparent base material, materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used. When a film substrate is used as the substrate, it is more preferable to use a substrate that is not optically distorted and a substrate having high transparency. Specific examples of the material include polyethylene terephthalate (PET), Examples thereof include polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.
  • PET polyethylene terephthalate
  • Examples of the plurality of conductive layers formed on the substrate include arbitrary conductive layers used for general circuit wiring or touch panel wiring.
  • Examples of the material for the conductive layer include metals and metal oxides.
  • Examples of the metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO 2 .
  • Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, and Mo.
  • At least one of the plurality of conductive layers includes a metal oxide.
  • the conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition part used in a capacitive touch panel or a wiring of a peripheral extraction part.
  • Circuit wiring formation board It is a board
  • a film substrate such as PET is preferably provided with a plurality of conductive layers such as metal oxides and metals.
  • ⁇ Exposure process (first exposure process)> The exposure process is performed in the first embodiment, and the first exposure process is performed in the second embodiment.
  • An example of the exposure process (first exposure process) is schematically shown in FIG.
  • the positive resist layer 14 is subjected to pattern exposure via the temporary support 12 of the photosensitive transfer material after the bonding step.
  • a mask 30 having a predetermined pattern is disposed above the photosensitive transfer material 100 disposed on the first conductive layer 24 (on the side opposite to the side in contact with the first conductive layer 24), and then For example, a method of exposing with ultraviolet rays from above the mask through the mask 30 may be used.
  • the detailed arrangement and specific size of the pattern are not particularly limited.
  • At least a part is preferably a fine wire of 100 ⁇ m or less, and more preferably 70 ⁇ m or less.
  • the light source used for exposure can be appropriately selected and used as long as it can irradiate light (for example, 365 nm, 405 nm, etc.) in a wavelength region where the exposed portion of the photosensitive transfer material can be dissolved in the developer. .
  • the exposure amount is preferably about 5 mJ / cm 2 to 200 mJ / cm 2 , more preferably about 10 mJ / cm 2 to 100 mJ / cm 2 . It is also preferable to perform heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure. By a process called PEB (Post Exposure Bake), pattern edge roughness due to standing waves generated in the resist layer during exposure can be reduced.
  • PEB Post Exposure Bake
  • the pattern exposure may be performed after the temporary support is peeled off from the intermediate layer and the resist layer, or before the temporary support is peeled off, it is exposed through the temporary support, and then the temporary support is removed. It may be peeled off. In order to prevent mask contamination due to contact between the intermediate layer and the mask, and to avoid the influence on the exposure caused by the foreign matter adhering to the mask, it is preferable to perform the 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.
  • ⁇ Development process (first development process)>
  • the developing step is performed, and in the second embodiment, the first developing step is performed.
  • An example of the development process (first development process) is schematically shown in FIG.
  • the development step after removing the temporary support 12 from the positive resist layer 14 after the exposure step (first exposure step), the positive resist layer 14 after the exposure step (first exposure step). Is developed to form the first pattern 14A.
  • the development process is a process of forming a pattern (first pattern) by developing the pattern-exposed positive resist layer.
  • the development of the pattern-exposed positive resist layer can be performed using a developer.
  • the developer is not particularly limited as long as the exposed portion of the positive resist layer can be removed.
  • a known developer such as the developer described in JP-A-5-72724 can be used. Specific examples include aqueous sodium hydroxide, aqueous potassium hydroxide, aqueous sodium carbonate, aqueous potassium carbonate, and aqueous tetramethylammonium hydroxide.
  • the developer is preferably a developer in which the exposed portion of the positive resist layer exhibits a dissolution type development behavior.
  • an alkaline aqueous developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is preferable.
  • the developer may further contain an organic solvent miscible with water, a surfactant, and the like.
  • Examples of the developer suitably used in the present disclosure include the developer described in Paragraph 0194 of International Publication No. 2015/092731.
  • the development method is not particularly limited and may be any of paddle development, shower development, shower and spin development, dip development, and the like.
  • the shower development will be described.
  • the exposed portion can be removed by spraying a developer onto the positive resist layer after exposure. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
  • the liquid temperature of the developer is preferably 20 ° C. to 40 ° C.
  • the post-baking process of heat-processing the pattern containing the resist layer obtained by image development.
  • the post-baking is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably in an environment of 506.6 kPa or more. On the other hand, it is more preferable to carry out in an environment of 114.6 kPa or less, and it is particularly preferable to carry out in an environment of 101.3 kPa or less.
  • the post-baking temperature is preferably 80 ° C. to 250 ° C., more preferably 110 ° C. to 170 ° C., and particularly preferably 130 ° C. to 150 ° C.
  • the post-baking time is preferably 1 to 30 minutes, more preferably 2 to 10 minutes, and particularly preferably 2 to 4 minutes.
  • the post-bake may be performed in an air environment or a nitrogen substitution environment.
  • the circuit wiring manufacturing method according to the present disclosure may include other processes such as a post-exposure process.
  • etching step (first etching step)> The etching process is performed in the first embodiment, and the first etching process is performed in the second embodiment.
  • An example of the etching process (first etching process) is schematically shown in FIG.
  • the etching process (first etching process)
  • at least the first conductive layer 24 and the second conductive layer 26 are etched among the plurality of conductive layers in the region where the first pattern 14A is not disposed.
  • the first conductive layer 24A and the second conductive layer 26A having the same pattern are formed by etching.
  • Etching of the conductive layer can be performed by a known method such as a method described in paragraphs 0048 to 0054 of JP 2010-152155 A or a dry etching method such as a known plasma etching.
  • etching method a commonly performed wet etching method in which the substrate is immersed in an etching solution can be used.
  • an etchant used for wet etching an acid type or alkaline type etchant may be appropriately selected according to an object to be etched.
  • acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and mixed aqueous solutions of acidic components and salts of ferric chloride, ammonium fluoride, potassium permanganate, and the like. Is done.
  • the acidic component a component obtained by combining a plurality of acidic components may be used.
  • alkaline type etchants include aqueous solutions of alkali components such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, salts of organic amines such as tetramethylammonium hydroxide, alkaline components and potassium permanganate. Examples thereof include a mixed aqueous solution of salt.
  • alkali component a component obtained by combining a plurality of alkali components may be used.
  • the temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower.
  • the first pattern used as an etching mask (etching pattern) in the present disclosure preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower. Therefore, the positive resist layer is prevented from being peeled off during the etching process, and the portion where the positive resist layer does not exist is selectively etched.
  • a cleaning process and a drying process may be performed as necessary to prevent contamination of the process line.
  • the cleaning process is performed by cleaning the substrate with pure water for 10 seconds to 300 seconds at room temperature, for example, and the drying process is performed using an air blow, for example, with an air blow pressure (about 0.1 kg / cm 2 to 5 kg / cm 2 ).
  • the drying may be performed by appropriately adjusting the above.
  • ⁇ Second exposure step> In the second embodiment, the second exposure process is performed. An example of the second exposure step is schematically shown in FIG. After the first etching step, pattern exposure is performed on the first pattern 14A after the first etching step with a pattern different from the first pattern.
  • the first pattern remaining on the first conductive layer is exposed at least at a portion corresponding to a portion to be removed of the first conductive layer in a second development step described later.
  • the same method as the pattern exposure in the first exposure step can be applied except that the mask 40 having a pattern different from that of the mask 30 used in the first exposure step is used.
  • the second development step is performed.
  • An example of the second developing process is schematically shown in FIG.
  • the first pattern 14A after the second exposure step is developed to form a second pattern 14B.
  • the exposed portion of the first pattern in the second exposure step is removed.
  • the same method as the development in the first development step can be applied.
  • the second exposure process is performed.
  • An example of the second etching step is schematically shown in FIG.
  • the second etching step at least the first conductive layer 24A is etched among the plurality of conductive layers in the region where the second pattern 14B is not disposed.
  • the same method as the etching in the first etching step can be applied except that an etching solution corresponding to the conductive layer to be removed by etching is selected.
  • the second etching step it is preferable to selectively etch fewer conductive layers than in the first etching step, depending on the desired pattern. For example, as shown in FIG. 2, the first conductive layer is etched by using an etchant that selectively etches only the first conductive layer 24B in a region where the positive resist layer is not disposed. The pattern can be different from the pattern of the conductive layer.
  • circuit wiring including conductive layers 24B and 26A having at least two types of patterns is formed.
  • ⁇ Positive resist layer removal process An example of the positive resist layer removing process is schematically shown in FIG. After the second etching step, the second pattern 14B remains on a part of the first conductive layer 24B. If the positive resist layer is unnecessary, all the remaining positive resist layer 14B may be removed.
  • a method of removing the remaining positive type resist layer The method of removing by chemical treatment can be mentioned.
  • a method for removing the positive resist layer for example, a substrate having a positive resist layer or the like in a stripping solution being stirred at preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 1 minute to 30 minutes. The method of immersing for a minute is mentioned.
  • the stripping solution examples include inorganic alkali components such as sodium hydroxide and potassium hydroxide, or organic alkali components such as primary amine, secondary amine, tertiary amine, and quaternary ammonium salt. , A stripping solution dissolved in dimethyl sulfoxide, N-methylpyrrolidone or a mixed solution thereof. A stripping solution may be used and stripped by a spray method, a shower method, a paddle method, or the like.
  • inorganic alkali components such as sodium hydroxide and potassium hydroxide
  • organic alkali components such as primary amine, secondary amine, tertiary amine, and quaternary ammonium salt.
  • a stripping solution may be used and stripped by a spray method, a shower method, a paddle method, or the like.
  • the circuit wiring manufacturing method according to the present disclosure may include other optional steps.
  • the following processes are mentioned, it is not limited to these processes.
  • the second embodiment may further include a step of attaching a light-transmitting protective film (not shown) on the first pattern after the first etching step and before the second exposure step. Good.
  • a light-transmitting protective film (not shown) on the first pattern after the first etching step and before the second exposure step.
  • the first pattern is subjected to pattern exposure via the protective film, and after the second exposure step, the protective film is peeled off from the first pattern, and then the second development step is performed.
  • the manufacturing method of the circuit wiring which concerns on this indication can include the process of reducing the visible light reflectance of some or all of the some conductive layers on a base material.
  • the treatment for reducing the visible light reflectance include an oxidation treatment.
  • visible light reflectance can be reduced by oxidizing copper to copper oxide and blackening.
  • paragraphs 0017 to 0025 of JP2014-150118A and paragraphs 0041, 0042, 0048 and 0058 of JP2013-206315A are described. The content of this publication is incorporated into the present disclosure.
  • the method for manufacturing a circuit wiring according to the present disclosure preferably 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.
  • the above-described second electrode pattern can be formed while being insulated from the first electrode pattern.
  • an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.
  • a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
  • the case where the circuit wiring having two different patterns is formed on the circuit wiring forming substrate including the two conductive layers has been described.
  • the number of conductive layers of the substrate to which the manufacturing method is applied is not limited to two layers, and a circuit wiring forming substrate in which three or more conductive layers are stacked is used, and the combination of the exposure step, the development step, and the etching step described above is used. By performing it three times or more, three or more conductive layers can be formed in different circuit wiring patterns.
  • the manufacturing method of the circuit wiring which concerns on this indication WHEREIN The base material has a some conductive layer in both surfaces, respectively, and the conductive layer formed in both surfaces of the base material It is also preferable to form circuits sequentially or simultaneously. With such a configuration, it is possible to form a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of the substrate and a second conductive pattern is formed on the other surface. Moreover, it is also preferable to form the circuit wiring for touch panels of such a structure from both surfaces of a base material by roll-to-roll.
  • the circuit wiring according to the present disclosure is a circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure.
  • the circuit board according to the present disclosure is a substrate having circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure.
  • the use of the circuit board concerning this indication is not limited, for example, it is preferred that it is a circuit board for touch panels.
  • the input device in the present disclosure is preferably a capacitive touch panel.
  • the display device according to the present disclosure preferably includes the input device according to the present disclosure.
  • the display device in the present disclosure is preferably an image display device such as an organic EL display device and a liquid crystal display device.
  • the touch panel according to the present disclosure is a touch panel having at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure.
  • the touch panel according to the present disclosure 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 disclosure is a touch panel display device having at least circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure, and is preferably a touch panel display device including the touch panel according to the present disclosure.
  • the method for manufacturing a touch panel or a touch panel display device according to the present disclosure preferably includes a method for manufacturing a circuit wiring according to the present disclosure.
  • the manufacturing method of the touch panel or the touch panel display device includes a step of bringing the resist layer of the photosensitive transfer material obtained by the method of manufacturing the photosensitive transfer material into contact with the substrate and bonding, and after the bonding step Pattern exposing the resist layer of the photosensitive transfer material, developing the resist layer after the pattern exposing step, forming a pattern, and etching the substrate in a region where the pattern is not disposed It is preferable that the process to include is included in this order.
  • the details of each process are synonymous with the details of each process in the above-described circuit wiring manufacturing method, and the preferred embodiments are also the same.
  • any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used.
  • the electrostatic capacity method is preferable.
  • the touch panel type a so-called in-cell type (for example, those described in FIGS. 5, 6, 7, and 8 of JP-T-2012-517051), a so-called on-cell type (for example, JP 2013-168125 A). 19 of the gazette, those described in FIGS.
  • JP 2012-89102 A OGS (One Glass Solution) type
  • TOL (Touch-on-Lens) type for example, JP No. 2013-54727 shown in FIG. 2
  • other configurations for example, those shown in FIG. 6 of JP2013-164671A
  • various out-cell types for example, GG, G1, G2, GFF, GF2, GF1, G1F, etc.
  • photosensitive transfer material means “second embodiment of the photosensitive transfer material” unless otherwise specified.
  • a second embodiment of the photosensitive transfer material according to the present disclosure includes a temporary support, an intermediate layer, and a photosensitive resin layer in this order, and the intermediate layer includes a water-soluble resin, particles, and an acidic group.
  • a polymer containing a structural unit having an acid group protected by a decomposable group is contained, and the photosensitive resin layer and the intermediate layer are in contact with each other.
  • the problem to be solved by the second embodiment of the photosensitive transfer material according to the present disclosure is to provide a photosensitive transfer material having excellent adhesion between the photosensitive resin layer and the intermediate layer.
  • the problems to be solved by the second embodiment of the photosensitive transfer material according to the present disclosure include a method of manufacturing a resin pattern, a method of manufacturing circuit wiring, and a method of manufacturing a touch panel using the photosensitive transfer material. Is to provide.
  • the photosensitive transfer material According to the second embodiment of the photosensitive transfer material according to the present disclosure, it is possible to provide a photosensitive transfer material having excellent adhesion between the photosensitive resin layer and the intermediate layer.
  • a method of manufacturing a resin pattern, a method of manufacturing circuit wiring, and a method of manufacturing a touch panel using the photosensitive transfer material are provided. Can do.
  • the photosensitive transfer material includes a positive photosensitive resin layer having a positive photosensitive resin layer containing a polymer containing a structural unit having an acid group protected by an acid-decomposable group. Transfer material.
  • the photosensitive resin layer is preferably a chemically amplified positive photosensitive resin layer.
  • the present inventors have found that when the photosensitive resin layer and the intermediate layer are provided in contact with each other, the adhesion between the photosensitive resin layer and the intermediate layer is not sufficient.
  • the present inventors have found that a photosensitive transfer material having excellent adhesion between the photosensitive resin layer and the intermediate layer can be obtained by using the photosensitive transfer material having the above-described configuration.
  • the intermediate layer is at least one selected from the group consisting of water-soluble resins, particles, and acidic groups, basic groups, anionic groups, and cationic groups.
  • the polar group is adsorbed on the particle surface, and the alkyl group having 6 or more carbon atoms is the photosensitive material. Adhesiveness between the photosensitive resin layer and the intermediate layer because the photosensitive resin layer and the intermediate layer are firmly adhered by penetrating into the resin layer or by hydrophobic interaction (hydrophobic effect) with the photosensitive resin layer. It is estimated to be excellent.
  • the photosensitive transfer material according to the present disclosure has an intermediate layer in contact with the photosensitive resin layer, and the intermediate layer includes a water-soluble resin, particles, an acidic group, a basic group, an anionic group, and a cationic group.
  • a polar compound having at least one polar group selected from the group consisting of and an alkyl group having 6 or more carbon atoms is contained.
  • the intermediate layer contains a polar compound having at least one 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 have a ring structure, but the adhesion between the photosensitive resin layer and the intermediate layer From the viewpoint of liquid stability in the properties, it is preferably a linear alkyl group or a branched alkyl group, and more preferably a linear alkyl group.
  • the alkyl group having 6 or more carbon atoms in the polar compound is preferably an alkyl group having 6 to 30 carbon atoms and an alkyl group having 8 to 22 carbon atoms from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer. And more preferably an alkyl group having 10 to 16 carbon atoms.
  • Examples of the polar group include primary to tertiary amino groups, primary to quaternary ammonium groups, pyridyl groups, pyridinium groups, and carboxylic acid groups from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer.
  • a quaternary ammonium base is a quaternary ammonium base.
  • a quaternary ammonium base is preferable.
  • the betaine structure which has a carboxylate structure and an ammonium structure, or the betaine structure which has a sulfonate structure and an ammonium structure is mentioned preferably, The betaine structure which has a sulfonate structure and an ammonium structure is mentioned more preferably.
  • the polar compound may form a salt with other compounds in the intermediate layer.
  • silica particles having an anionic silanol group on the surface and an amine compound are used, even if the amino group in the amine compound partially reacts with the silanol group to form a salt Good.
  • the amine compound contained in the intermediate layer is generated in two types: a compound having an amino group and a compound having an ammonium base.
  • the polar group is defined as at least one 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 one polar group or two or more polar groups, but the adhesion between the photosensitive resin layer and the intermediate layer, and the intermediate layer forming composition From the viewpoint of liquid stability, a compound having only one polar group is preferable.
  • the said betaine structure shall count as one combining a cation site
  • the counter anion in the primary to quaternary ammonium base or the pyridinium group is not particularly limited, but preferably includes a monovalent anion, and includes a halide ion or a hydroxide ion. It is more preferable that it contains a chloride ion or a hydroxide ion.
  • the counter cation in the carboxylate group, the sulfonate group, the phosphonate group, or the phosphate group is not particularly limited, but preferably contains a monovalent cation, an alkali metal ion, or More preferably, it contains primary to quaternary ammonium ions.
  • the polar compound may be an aliphatic compound or an aromatic compound, but from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer, and liquid stability in the intermediate layer forming composition.
  • An aliphatic compound is preferable.
  • the molecular weight of the polar compound is not particularly limited, but is preferably 100 to 800 from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer, and liquid stability in the intermediate layer forming composition, More preferably, it is 120 to 600, and particularly preferably 150 to 400.
  • polar compound examples include, for example, primary to tertiary amino compounds, primary to quaternary ammonium salt compounds, carboxylic acid compounds, sulfonic acid compounds, carboxylate compounds, sulfonate compounds, etc. Is mentioned.
  • the intermediate layer may contain the above polar compound singly or in combination of two or more.
  • middle layer is 0.01 with respect to the total mass of an intermediate
  • the intermediate layer contains particles.
  • the particles are preferably metal oxide particles or organic particles, and oxide particles of an element selected from the group consisting of Si, Ti and Zr Or it is more preferable that it is an organic particle.
  • the metal of the metal oxide particles in the present disclosure includes metalloids such as B, Si, Ge, As, Sb, and Te.
  • metal oxide particles Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B Oxide particles containing atoms such as Al, Si, Ge, Sn, Pb, Sb, Bi, Te, etc. are preferred, silica, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide, or Antimony / tin oxide is more preferable, silica, titanium oxide, titanium composite oxide, or zirconium oxide is more preferable, silica, titanium oxide, or zirconium oxide is particularly preferable, and silica is most preferable.
  • organic resin particles are preferably exemplified.
  • the organic resin particles include homopolymers and copolymers of acrylic acid monomers such as acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester, and cellulose polymers such as nitrocellulose, methylcellulose, ethylcellulose, and cellulose acetate.
  • acrylic resin particles are preferable as the organic particles, and polymethyl methacrylate particles are more preferable.
  • silica particles are particularly preferable from the viewpoint of adhesion between the intermediate layer and the photosensitive layer.
  • the surface of these particles can be treated with an organic material or an inorganic material in order to impart dispersion stability.
  • the particles are preferably particles having a hydrophilic surface.
  • the surface of particles having a hydrophobic surface may be subjected to a hydrophilic treatment.
  • the particles are particles having an anionic group or a cationic group on the surface from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer and liquid stability in the intermediate layer forming composition.
  • the particles having an anionic group on the surface are more preferable, and the silica particles having an anionic group on the surface are particularly preferable.
  • the intermediate layer is a particle having an anionic group on the surface, from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer
  • the polar compound is a polar compound having a basic group or a cationic group. Preferably there is.
  • the said polar compound is a polar compound which has an acidic group or an anionic group from an adhesive viewpoint of the photosensitive resin layer and an intermediate
  • grain has on the surface a silanol group or a carboxy group is mentioned preferably, A silanol group is mentioned more preferably.
  • the cationic group that the particles have on the surface is preferably an amino group.
  • the arithmetic average particle diameter of the above particles is preferably 100 nm or less, more preferably 50 nm or less, still more preferably 6 nm to 30 nm, from the viewpoint of the adhesion between the intermediate layer and the photosensitive layer. It is particularly preferable that the thickness is ⁇ 25 nm.
  • the method for measuring the arithmetic average particle diameter of the particles in the present disclosure refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the maximum diameter is taken as the diameter.
  • the intermediate layer may contain the above particles alone or in combination of two or more.
  • the content of the particles in the intermediate layer is preferably 1% by mass to 90% by mass with respect to the total mass of the intermediate layer from the viewpoint of adhesion between the intermediate layer and the photosensitive layer, and preferably 3% by mass to 70% by mass. % Is more preferable, and 5% by mass to 50% by mass is particularly preferable.
  • the intermediate layer contains a water-soluble resin.
  • water-soluble means that the solubility in 100 g of water having a pH of 7.0 at 22 ° C. is 0.1 g or more.
  • the water-soluble resin has a solubility in 100 g of water having a pH of 7.0 at 22 ° C. of preferably 1 g or more, and more preferably 5 g or more.
  • water-soluble resins 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. It is done. Among these, a cellulose resin is preferable, and at least one resin selected from the group consisting of hydroxypropylcellulose and hydroxypropylmethylcellulose is more preferable.
  • the intermediate layer may contain one type of water-soluble resin, or may contain two or more types.
  • the content of the water-soluble resin is preferably 10% by mass to 99% by mass and preferably 30% by mass to 97% by mass with respect to the total mass of the intermediate layer from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer. More preferably, it is more preferably 50% by mass to 95% by mass.
  • the intermediate layer preferably contains a pH-sensitive dye having a maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development of 450 nm or more and the maximum absorption wavelength changing depending on pH.
  • “Maximum absorption wavelength changes” means a mode in which a dye in a colored state is decolored, a mode in which a dye in a decolored state is colored, and a color in a colored state changes to a colored state in another hue It may refer to any aspect of the aspects.
  • the pH-sensitive dye is more preferably a latent dye that is decolored by an acid generated from the photoacid generator.
  • Confirmation of the pH-sensitive dye can be performed by the following method.
  • Titrate with a 0.01 mol / L (0.01 N) aqueous sodium hydroxide solution to confirm the color change and the pH when the color change appears.
  • the pH is a value measured at 25 ° C. using a pH meter (model number: HM-31, manufactured by Toa DKK Co., Ltd.).
  • the measurement method of the maximum absorption wavelength in the present disclosure is to measure a transmission spectrum in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) at 25 ° C. in an air atmosphere. The wavelength at which the light intensity is minimized (maximum absorption wavelength) is measured.
  • Examples of the dye that can be erased by exposure include leuco compounds, diphenylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, anthraquinone dyes, and the like.
  • a leuco compound is preferable from the viewpoint of visibility.
  • leuco compounds include leuco compounds such as triarylmethane (for example, triphenylmethane), spiropyran, fluorane, diphenylmethane, rhodamine lactam, indolylphthalide, and leucooramine.
  • a leuco compound (triarylmethane dye) having a triarylmethane skeleton is preferable, and a triphenylmethane dye is more preferable.
  • the leuco compound preferably has a lactone ring, a sultin ring, or a sultone ring, and the lactone ring, sultin ring, or sultone ring is preferably opened or closed, and has a sultone ring.
  • the pigment is preferably a water-soluble compound for the purpose of preventing defects due to pigment deposition.
  • the solubility of the dye in 100 g of water having a pH of 7.0 at 22 ° C. is preferably 1 g or more, and more preferably 5 g or more.
  • middle layer may contain the pigment
  • the content of the pigment in the intermediate layer is preferably 0.01% by mass to 10% by mass, and preferably 0.5% by mass to 5% by mass with respect to the total mass of the intermediate layer from the viewpoint of visibility. More preferably, the content is 1.0% by mass to 3.0% by mass.
  • the intermediate layer preferably contains a surfactant from the viewpoint of thickness uniformity.
  • a surfactant having a fluorine atom 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.
  • a surfactant having a fluorine atom is preferable from the viewpoint of suppressing generation of streaks in the photosensitive resin layer and the intermediate layer and adhesion, and a perfluoroalkyl group and a polyalkyleneoxy are preferable.
  • a surfactant having a group is more preferable.
  • any of anionic, cationic, nonionic (nonionic), or amphoteric can be used, but a preferable surfactant is a nonionic surfactant.
  • the surfactant preferably has a solubility of 1 g or more in 100 g of water at 25 ° C. from the viewpoint of suppressing the precipitation of the surfactant.
  • the intermediate layer may contain one kind of surfactant, or two or more kinds.
  • the content of the surfactant in the intermediate layer is from 0.05% by mass to 2.0% with respect to the total mass of the intermediate layer, from the viewpoint of suppressing the occurrence of streaks in the photosensitive resin layer and the intermediate layer, and adhesion.
  • the mass is preferably 0.1% by mass, more preferably 0.1% by mass to 1.0% by mass, and particularly preferably 0.2% by mass to 0.5% by mass.
  • the intermediate layer can contain a pH adjusting agent.
  • the pH adjuster By including the pH adjuster, the coloring state or decoloring state of the dye in the intermediate layer can be more stably maintained, and the adhesion between the photosensitive resin layer and the intermediate layer is further improved.
  • the average thickness of the intermediate layer is preferably from 0.3 ⁇ m to 10 ⁇ m, more preferably from 0.3 ⁇ m to 5 ⁇ m, more preferably from 0.3 ⁇ m to 0.3 ⁇ m, from the viewpoints of adhesion between the photosensitive resin layer and the intermediate layer and pattern formability. 3 ⁇ m is particularly preferable. Moreover, it is preferable that the average thickness of an intermediate
  • the intermediate layer in the present disclosure can be formed by preparing a composition for forming an intermediate layer containing a component used for forming the intermediate layer and a water-soluble solvent, and applying and drying the composition. It is also possible to prepare a composition by dissolving each component in a solvent in advance and then mixing the resulting solution at a predetermined ratio.
  • the composition prepared as described above may be filtered using a filter having a pore size of 3.0 ⁇ m.
  • the intermediate layer can be formed on the temporary support by applying the intermediate layer-forming composition to the temporary support and drying it.
  • the coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
  • composition for forming an intermediate layer contains the component used for formation of an intermediate
  • An intermediate layer can be suitably formed by adding a water-soluble solvent to each component, adjusting the viscosity, and applying and drying.
  • water-soluble solvent known water-soluble solvents can be used, and examples thereof include water, alcohols having 1 to 6 carbon atoms, and preferably contains water. 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 these, it is preferable to use at least one selected from the group consisting of methanol, ethanol, n-propanol, and isopropanol.
  • the photosensitive transfer material has an adhesive property between the photosensitive resin layer and the intermediate layer, and an adhesive property between the temporary support and the intermediate layer. It is preferable to further have a water-soluble resin layer having a particle content of 5% by mass or less.
  • the water-soluble resin layer may be a layer containing a water-soluble resin and having a particle content of 5% by mass or less, and the particle content is 0% by mass, that is, even if the particle is not included. Good.
  • the water-soluble resin layer preferably has a smaller content of particles than the intermediate layer from the viewpoints of storage stability and adhesion between the photosensitive resin layer and the intermediate layer.
  • the water-soluble resin layer preferably contains the above polar compound.
  • the polar compound in the water-soluble resin layer is intermediated. It is preferable to diffuse into the layer and form an intermediate layer containing the polar compound and particles from the viewpoint of the storage stability of the liquid and the adhesion between the photosensitive resin layer and the intermediate layer.
  • the water-soluble resin layer contains a water-soluble resin.
  • the water-soluble resin used for the water-soluble resin layer can be the same as the water-soluble resin used for the intermediate layer described above, and the preferred embodiment is also the same.
  • the water-soluble resin layer may contain one type of water-soluble resin, or may contain two or more types.
  • the content of the water-soluble resin is preferably 50% by mass to 100% by mass with respect to the total mass of the water-soluble resin layer, from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer, and preferably 65% by mass to It is more preferably 99% by mass, and particularly preferably 80% by mass to 98% by mass.
  • the water-soluble resin layer may contain particles as long as the content is 5% by mass or less.
  • the particles used for the water-soluble resin layer can be the same as the particles used for the intermediate layer described above, and the preferred embodiments are also the same.
  • the water-soluble resin layer may contain one kind of particles or two or more kinds.
  • the content of the particles is preferably 3% by mass or less and more preferably 1% by mass or less with respect to the total mass of the water-soluble resin layer from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer. preferable.
  • the water-soluble resin layer may contain a polar compound.
  • the polar compound used for the water-soluble resin layer can be the same as the polar compound used for the intermediate layer described above, and the preferred embodiment is also the same.
  • the water-soluble resin layer may contain one kind of polar compound or two or more kinds.
  • the content of the polar compound is 0.01% by mass with respect to the total mass of the water-soluble resin layer, from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer and liquid stability in the intermediate layer forming composition. Is preferably 5% by mass, more preferably 0.05% by mass to 2% by mass, further preferably 0.1% by mass to 1.0% by mass, and more preferably 0.2% by mass to It is especially preferable that it is 0.8 mass%.
  • the water-soluble resin layer may contain other compounds other than those described above. There is no restriction
  • the average thickness of the water-soluble resin layer is preferably from 0.3 ⁇ m to 10 ⁇ m, more preferably from 0.3 ⁇ m to 5 ⁇ m, from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation. Particularly preferred is 3 ⁇ m to 2.5 ⁇ m.
  • the average thickness of the water-soluble resin layer is preferably larger than the average thickness of the intermediate layer from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation.
  • ⁇ Method for forming water-soluble resin layer There is no restriction
  • the intermediate layer-forming composition For example, some of the particles in the intermediate layer-forming composition move to the water-soluble resin layer, and part of the polar compound contained in the water-soluble resin layer is the intermediate layer-forming composition, that is, Move to the middle layer.
  • the water-soluble resin layer may be a layer that contains particles, and a particle-containing layer that does not contain the polar compound may be formed.
  • the particle-containing layer is a layer containing the polar compound.
  • the water-soluble resin layer forming composition used for forming the water-soluble resin layer may or may not contain particles. It is preferable that no particles are contained. Moreover, it is preferable that the composition for water-soluble resin layer formation used for formation of the said water-soluble resin layer contains a polar compound from a liquid-stable viewpoint of the composition for water-soluble resin layer formation.
  • the intermediate layer forming composition used for forming the intermediate layer may or may not contain the polar compound. From the viewpoint of the liquid stability of the layer forming composition, it is preferable not to contain the polar compound.
  • 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 particles is small.
  • a water-soluble resin layer can be suitably formed by adding a water-soluble solvent to each component, adjusting the viscosity, and applying and drying.
  • the photosensitive transfer material according to the present disclosure has a photosensitive resin layer.
  • the photosensitive resin layer in the present disclosure is a positive photosensitive resin layer.
  • the photosensitive resin layer used in the present disclosure includes an acid-decomposable resin, that is, a polymer having a structural unit having an acid group protected by an acid-decomposable group, and photoacid generation from the viewpoint of sensitivity and resolution.
  • a chemically amplified positive photosensitive resin layer containing an agent is preferable.
  • Photo acid generators such as onium salts and oxime sulfonate compounds described below are produced as a catalyst for the deprotection of protected acid groups in the polymer, as the acid generated in response to actinic radiation (active light).
  • the acid generated by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as the power of 10, which is a so-called chemical amplification.
  • a large value such as the power of 10
  • chemical amplification As a result, high sensitivity is obtained.
  • a quinonediazide compound is used as a photoacid generator sensitive to actinic rays, a carboxy group is generated by a sequential photochemical reaction, but its quantum yield is always 1 or less and does not correspond to a chemical amplification type.
  • the photosensitive resin layer includes a polymer X (also simply referred to as “polymer X”) having a structural unit A having an acid group protected by an acid-decomposable group (also simply referred to as “structural unit A”). It is preferable.
  • the photosensitive resin layer may contain another polymer.
  • the polymer X having the structural unit A and other polymers are collectively referred to as “polymer component”.
  • an acid group protected by an acid-decomposable group in the polymer X undergoes a deprotection reaction to be an acid group by the action of an acidic substance such as a catalytic amount of acid generated by exposure.
  • This acid group enables the photosensitive resin layer to be dissolved in the 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.
  • structural unit A preferred embodiments of the structural unit A will be described.
  • the polymer component preferably includes a polymer X having a structural unit A having an acid group protected with an acid-decomposable group.
  • the photosensitive resin layer contains the polymer X having the structural unit A, it can be an extremely sensitive chemical amplification positive type photosensitive resin layer.
  • Known acid groups and acid-decomposable groups in the present disclosure can be used, and are not particularly limited. Specific examples of the acid group preferably include a carboxy group and a phenolic hydroxyl group.
  • the acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal-type protecting group such as 1-alkoxyalkyl group, tetrahydropyranyl group, or tetrahydrofuranyl group) or an acid-decomposable group.
  • an acid for example, an acetal-type protecting group such as 1-alkoxyalkyl group, tetrahydropyranyl group, or tetrahydrofuranyl group
  • difficult groups for example, tertiary alkyl groups such as tert-butyl group and tertiary alkyloxycarbonyl groups such as tert-butyloxycarbonyl group (carbonate-type protecting group).
  • the acid-decomposable group is preferably a group having a structure protected in the form of an acetal.
  • the acid-decomposable group is preferably an acid-decomposable group having a molecular weight of 300 or less from the viewpoint of suppressing variations in the line width of the conductive wiring when applied to the formation of a conductive pattern.
  • the polymer X contained in the photosensitive resin layer may be one type or two or more types.
  • the structural unit A having an acid group protected with an acid-decomposable group is preferably a structural unit represented by the following formula A1, formula A2 or formula A3 from the viewpoint of sensitivity and resolution.
  • R 11 and R 12 each independently represents a hydrogen atom, an alkyl group or an aryl group, at least one of R 11 and R 12 is an alkyl group or an aryl group, and R 13 is an alkyl group or an aryl group.
  • R 11 or R 12 and R 13 may be linked to form a cyclic ether
  • R 14 represents a hydrogen atom or a methyl group
  • X 1 represents a single bond or a divalent linking group.
  • R 15 represents a substituent
  • n represents an integer of 0 to 4.
  • R 21 and R 22 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 21 and R 22 is an alkyl group or an aryl group, and R 23 is an alkyl group or an aryl group.
  • R 21 or R 22 and R 23 may be linked to form a cyclic ether, and each R 24 independently represents a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, or an aryl group.
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group or an aryl group.
  • R 31 or R 32 and R 33 may be linked to form a cyclic ether
  • R 34 represents a hydrogen atom or a methyl group
  • X 0 represents a single bond or a divalent linking group.
  • R 31 or R 32 when R 31 or R 32 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R 31 or R 32 is an aryl group, a phenyl group is preferable. R 31 and R 32 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 33 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Further, the alkyl group and aryl group in R 31 to R 33 may have a substituent.
  • R 31 or R 32 and R 33 may be linked to form a cyclic ether, and R 31 or R 32 and R 33 are preferably linked to form a cyclic ether.
  • the number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
  • X 0 represents a single bond or an arylene group, and a single bond is preferable.
  • the arylene group may have a substituent.
  • the structural unit A represented by the formula A3 is a structural unit having a carboxy group protected with an acetal 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 more excellent.
  • R 34 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the glass transition temperature (Tg) of the polymer X can be further lowered. More specifically, the structural unit in which R 34 in Formula A3 is a hydrogen atom is preferably 20% by mass or more based on the total amount of the structural unit A contained in the polymer X.
  • the content (content ratio: mass ratio) of the structural unit in which R 34 in formula A3 is a hydrogen atom in the structural unit A is calculated by a conventional method from 13 C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of the peak intensity.
  • the acid-decomposable group is preferably a group having a cyclic structure, more preferably a tetrahydrofuran ring or a group having a tetrahydropyran ring structure, and more preferably a tetrahydrofuran ring structure from the viewpoint of sensitivity. It is more preferably a group, and particularly preferably a tetrahydrofuranyl group.
  • the structural unit A contained in the polymer X may be one type or two or more types.
  • the content of the structural unit A in the polymer X is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 50% by mass, with respect to the total mass of the polymer component. More preferably, it is 40% by mass. If it is within the above range, the resolution is further improved.
  • the content of the structural unit A represents the total content of the two or more structural units A.
  • the content (content ratio: mass ratio) of the structural unit A in the polymer component can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from 13 C-NMR measurement.
  • the polymer X may include a structural unit B having an acid group (also simply referred to as “structural unit B”).
  • the structural unit B is a structural unit having an acid group that is not protected by an acid-decomposable group, that is, an acid group that does not have a protective group.
  • the acid group in this specification means a proton dissociable group having a pKa of 12 or less.
  • the pKa of the acid group is preferably 10 or less, more preferably 6 or less, from the viewpoint of improving sensitivity.
  • the pKa of the acid group is preferably ⁇ 5 or more.
  • the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group. Among these, a carboxy group or a phenolic hydroxyl group is preferable, and a carboxy group is more preferable.
  • the structural unit B contained in the polymer X may be only one type or two or more types.
  • the content of the structural unit B in the polymer X is preferably 0.01% by mass to 20% by mass and more preferably 0.01% by mass to 10% by mass with respect to the total mass of the polymer component. More preferably, the content is 0.1 mass% to 5 mass%. If it is in the above range, the resolution will be better.
  • the content of the structural unit B represents the total content of the two or more structural units B.
  • the content (content ratio: mass ratio) of the structural unit B in the polymer X can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from 13 C-NMR measurement.
  • structural unit C also simply referred to as “structural unit C”
  • structural unit C other than the structural unit A and the structural unit B described above. It is preferable to contain.
  • styrenes (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester , Bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, groups having an aliphatic cyclic skeleton, other Mention may be made of saturated compounds.
  • the polymer X can be adjusted by adjusting at least one of the kind and the content using the structural unit C.
  • the Tg, acid value, and hydrophilicity / hydrophobicity of the polymer X can be easily adjusted.
  • the polymer X may contain only 1 type of structural unit C, or may contain 2 or more types.
  • the structural unit C is styrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, methyl (meth) acrylate, (meth) acrylic.
  • the structural unit C preferably includes a structural unit having a basic group from the viewpoint of resolution.
  • the basic group include groups 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 a primary amino group, a secondary amino group, or a tertiary amino group, but from the viewpoint of resolution, a secondary amino group or Tertiary amino groups are preferred.
  • the monomer that forms the structural unit having a basic group include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2- (dimethylamino) ethyl methacrylate, acrylic acid 2 , 2,6,6-Tetramethyl-4-piperidyl, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, methacrylic acid 2- (diethylamino) ethyl, 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate, N- (3-diethylamino) propyl methacrylate, N- (3-diethylamino) propyl acrylate, 2-methacrylic acid 2- Diis
  • a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton is preferable from the viewpoint of improving the electrical characteristics of the obtained transfer material.
  • monomers that form these structural units include styrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and Examples thereof include benzyl (meth) acrylate, and cyclohexyl (meth) acrylate is preferably used.
  • (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion.
  • (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion.
  • Specific examples 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 represents the total content of the two or more structural units C.
  • the preferable example of the polymer X in this indication is given, this indication is not limited to the following illustrations.
  • the ratio of the structural unit and the weight average molecular weight in the following exemplary compounds are appropriately selected in order to obtain preferable physical properties.
  • the glass transition temperature (Tg) of the polymer X in the present disclosure is preferably 90 ° C. or lower, more preferably 20 ° C. or higher and 60 ° C. or lower, and 30 ° C. or higher and 50 ° C. or lower. More preferably it is.
  • the FOX formula can be calculated from the Tg of the homopolymer of each constituent unit of the target polymer and the mass ratio of each constituent unit. Using the guideline, it is possible to control the Tg of the target polymer.
  • the FOX formula will be described below. Tg of the homopolymer of the first structural unit contained in the polymer is Tg1, the mass fraction in the copolymer of the first structural unit is W1, and the Tg of the homopolymer of the second structural unit is Tg2.
  • the Tg0 (K) of the copolymer containing the first structural unit and the second structural unit is in accordance with the following formula: It is possible to estimate.
  • FOX formula: 1 / Tg0 (W1 / Tg1) + (W2 / Tg2)
  • a copolymer having a desired Tg can be obtained by adjusting the type and mass fraction of each constituent unit contained in the copolymer using the FOX formula described above. It is also possible to adjust the Tg of the polymer by adjusting the weight average molecular weight of the polymer.
  • the acid value of the polymer X is preferably from 0 mgKOH / g to 50 mgKOH / g, more preferably from 0 mgKOH / g to 20 mgKOH / g, and more preferably from 0 mgKOH / g to 10 mgKOH / g from the viewpoint of resolution. More preferably, it is g or less.
  • the acid value of the polymer X is preferably 10 mgKOH / g or less, more preferably 3 mgKOH / g or less, from the viewpoint of storage stability and adhesion between the photosensitive resin layer and the intermediate layer. preferable.
  • the acid value of the polymer in the present disclosure represents the mass of potassium hydroxide required to neutralize the acidic component per gram of polymer.
  • the solution was neutralized and titrated with a 0.1 mol / L aqueous sodium hydroxide solution at 25 ° C.
  • the acid value is 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
  • Vs Amount of 0.1 mol / L sodium hydroxide aqueous solution required for titration (mL)
  • f Potency of 0.1 mol / L sodium hydroxide aqueous solution
  • the molecular weight of the polymer X is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight.
  • the weight average molecular weight of the polymer X is preferably 2,000 to 60,000, and more preferably 3,000 to 50,000.
  • the ratio (dispersion degree) between the number average molecular weight and 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 disclosure can be measured by GPC (gel permeation chromatography), and as a measuring device, various commercially available devices can be used. Known measurement techniques can be used.
  • GPC gel permeation chromatography
  • HLC registered trademark
  • -8220GPC manufactured by Tosoh Corp.
  • TSKgel registered trademark
  • Super HZM-M 4 .6 mm ID ⁇ 15 cm, manufactured by Tosoh Corp.
  • Super HZ4000 4 mm ID ⁇ 15 cm, manufactured by Tosoh Corp.
  • Super HZ3000 4.6 mm ID ⁇ 15 cm, manufactured by Tosoh Corp.
  • Super HZ2000 4.6 mm ID
  • THF tetrahydrofuran
  • the measurement conditions are as follows: the sample concentration is 0.2% by mass, the flow rate is 0.35 ml / min, the sample injection amount is 10 ⁇ L, the measurement temperature is 40 ° C., and a differential refractive index (RI) detector is used. be able to.
  • the calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “ It can be produced using any of the seven samples of “A-2500” and “A-1000”.
  • the production method (synthetic method) of the polymer X is not particularly limited.
  • the photosensitive resin layer in the present disclosure preferably contains the polymer component in a proportion of 50% by mass to 99.9% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of adhesion, and is 70% by mass. More preferably, it is contained in a proportion of -98% by mass.
  • the photosensitive resin layer preferably contains the polymer X in a proportion of 50% by mass to 99.9% by mass with respect to the total mass of the photosensitive resin layer, and is preferably 70% by mass to 98%. More preferably, it is contained in a proportion by mass.
  • the photosensitive resin layer does not contain a constituent unit having an acid group protected with an acid-decomposable group as long as the polymer component does not impair the effect of the photosensitive transfer material according to the present disclosure in addition to the polymer X. It may further contain a polymer (also referred to as “other polymer”). Unless otherwise specified, the polymer component in the present disclosure means a polymer including other polymers added in addition to the polymer X. In addition, even if it is a high molecular compound, the compound applicable to the crosslinking agent, a dispersing agent, and surfactant mentioned later shall not be contained in a polymer component.
  • the content of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less in the total polymer component, More preferably, it is at most mass%.
  • the photosensitive resin layer may contain only one type of other polymer, or may contain two or more types.
  • polyhydroxystyrene can be used, which are commercially available, such as SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer).
  • ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncryl 690, Joncryl 6 Joncryl 67, Joncryl 586 (manufactured by BASF) or the like can also be used.
  • the photosensitive resin layer contains a photoacid generator.
  • the photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiating active rays such as ultraviolet rays, far ultraviolet rays, X-rays, and electron beams.
  • the photoacid generator used in the present disclosure is preferably a compound that generates an acid in response to an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but its chemical structure is not limited.
  • a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
  • the photoacid generator used in the present disclosure is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a pKa of 2 or less.
  • a photoacid generator that generates an acid is particularly preferable.
  • the lower limit value of pKa is not particularly defined, but is preferably ⁇ 10.0 or more, for example.
  • Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.
  • Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, quaternary ammonium salts, and the like. Of these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.
  • ionic photoacid generator ionic photoacid generators described in paragraphs 0114 to 0133 of JP 2014-85643 A can also be preferably used.
  • nonionic photoacid generators examples include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds.
  • the photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion.
  • Specific examples of the trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds include the compounds described in paragraphs 0083 to 0088 of JP2011-221494A.
  • oxime sulfonate compound those described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 can be suitably used.
  • the photoacid generator preferably includes at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and more preferably includes an oxime sulfonate compound from the viewpoint of sensitivity and resolution. .
  • the photoacid generator of the following structures is mentioned, for example.
  • the photosensitive resin layer may contain 1 type of photo-acid generators individually, and may contain 2 or more types.
  • the content of the photoacid generator in the photosensitive resin layer is preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of sensitivity and resolution. More preferably, the content is 5% by mass to 5% by mass.
  • the photosensitive resin layer in the present disclosure may contain other additives as necessary in addition to the polymer X, the photoacid generator, and the solvent.
  • additives known ones can be used, and examples thereof include a plasticizer, a sensitizer, a heterocyclic compound, an alkoxysilane compound, a basic compound, a rust inhibitor, and a surfactant.
  • plasticizer, sensitizer, heterocyclic compound, and alkoxysilane compound include those described in paragraphs 0097 to 0119 of WO2018 / 179640.
  • the photosensitive resin layer in the photosensitive transfer material according to the present disclosure may contain 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 more preferably 1% by mass or less with respect to the total mass of the photosensitive resin layer. Further preferred.
  • the photosensitive resin layer further contains a basic compound.
  • the basic compound can be arbitrarily selected from basic compounds used in 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 JP-A-2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
  • As the basic compound N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea (CMTU) can be preferably used. Moreover, as a commercial item of CMTU, the thing by Toyo Kasei Kogyo Co., Ltd. is mentioned.
  • a benzotriazole compound is preferable from the viewpoint of linearity of the conductive wiring when applied to the 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- Pyridinyl) benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-ethylbenzotriazole, 1- (1′-hydroxyethyl) benzotriazole, 1- (2′-hydroxyethyl) benzotriazole, 1-propyl Benzoto Azole, 1- (1′-hydroxypropyl) benzotriazole, 1- (2′-hydroxypropyl) benzotriazole, 1- (3′-hydroxypropyl) benzotriazole, 4-hydroxy-1H-benzotriazole, 5-methyl -1H-benzotriazole, methylbenzotriazole-5-carboxylate, ethylbenzotriazole-5-carboxylate,
  • the photosensitive resin layer may contain one type of basic compound or two or more types.
  • the content of the basic compound is preferably 0.001% by mass to 5% by mass and more preferably 0.005% by mass to 3% by mass with respect to the total mass of the photosensitive resin layer.
  • the photosensitive resin layer contains a surfactant from the viewpoint of thickness uniformity.
  • the surfactant include anionic, cationic, nonionic (nonionic), and amphoteric surfactants.
  • a preferred surfactant is a nonionic surfactant.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. .
  • the surfactant for example, the surfactants described in paragraphs 0120 to 0125 of WO2018 / 179640 can be used. Further, as a commercially available surfactant, for example, Megafac F-552 or F-554 (above, manufactured by DIC Corporation) can be used. In addition, surfactants described in Japanese Patent No. 4502784, paragraph 0017 and Japanese Patent Application Laid-Open No. 2009-237362, paragraphs 0060 to 0071 can also be used.
  • the photosensitive resin layer may contain one type of surfactant, or two or more types.
  • the content of the surfactant is preferably 0.001% by mass to 10% by mass and more preferably 0.01% by mass to 3% by mass with respect to the total mass of the photosensitive resin layer.
  • metal oxide particles an antioxidant, a dispersant, an acid proliferation agent, a development accelerator, a conductive fiber, a colorant, a thermal radical polymerization initiator
  • known additives such as a thermal acid generator, an ultraviolet absorber, a thickener, a crosslinking agent, and an organic or inorganic suspending agent can be further added. Preferred embodiments of these components are described in paragraphs 0165 to 0184 of JP-A-2014-85643, respectively, and the contents of this publication are incorporated herein.
  • the average thickness of the photosensitive resin layer is preferably 0.5 ⁇ m to 20 ⁇ m.
  • the average thickness of the photosensitive resin layer is more preferably 0.8 ⁇ m to 15 ⁇ m, and particularly preferably 1.0 ⁇ m to 10 ⁇ m.
  • the average thickness of each layer is measured by observing a cross section in a direction perpendicular to the surface direction of the transfer material with a scanning electron microscope (SEM). The average thickness is the average value of 10 or more thicknesses measured.
  • the photosensitive resin layer in the present disclosure can be formed by preparing a photosensitive resin composition containing a component used for forming the photosensitive resin layer and a solvent, and applying and drying the composition. It is also possible to prepare a composition by preparing each component in a solution previously dissolved in a solvent and then mixing the resulting solution at a predetermined ratio. The composition prepared as described above may be filtered using, for example, a filter having a pore size of 0.2 ⁇ m to 30 ⁇ m.
  • the photosensitive resin layer in this indication can be formed by apply
  • the coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating. Moreover, after forming the below-mentioned intermediate
  • the photosensitive resin composition contains the component used for formation of the photosensitive resin layer, and a solvent.
  • the photosensitive resin layer can be suitably formed by adding a solvent to each component, adjusting the viscosity, and applying and drying.
  • solvent known solvents can be used, and for example, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 can be used.
  • a solvent having a vapor pressure of 1 kPa to 16 kPa at 20 ° C. described in paragraph 0014 of JP-A-2018-177889 can be preferably used.
  • the solvent which can be used for this indication may be used individually by 1 type, and may use 2 types together.
  • the content of the solvent in applying the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition, and 100 parts by mass. More preferably, it is 900 parts by mass.
  • the photosensitive transfer material according to the present disclosure has a temporary support.
  • the temporary support is a support that supports the photosensitive resin layer and can be peeled off.
  • the temporary support used in the present disclosure preferably has light transmittance from the viewpoint that the photosensitive resin layer can be exposed through the temporary support when the photosensitive resin layer is subjected to pattern exposure. Having light transmittance means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of light used for pattern exposure is a viewpoint of improving exposure sensitivity. Therefore, 60% or more is preferable, and 70% or more is more preferable.
  • Examples of the method for measuring the transmittance include a method of measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
  • Examples of the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is particularly preferable from the viewpoints of strength and flexibility.
  • 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 average thickness of the temporary support is not particularly limited, but is preferably in the range of 5 ⁇ m to 200 ⁇ m, and more preferably in the range of 10 ⁇ m to 150 ⁇ m in terms of ease of handling and versatility.
  • the thickness of the temporary support depends on the material in terms of strength as a support, flexibility required for bonding with a circuit wiring forming substrate, light transmittance required in the first exposure process, etc. Just choose.
  • a preferred embodiment of the temporary support is described, for example, in paragraphs 0017 to 0018 of JP 2014-85643 A, and the contents of this publication are incorporated in the present disclosure.
  • the photosensitive transfer material according to the present disclosure preferably has a cover film on the surface of the photosensitive transfer material opposite to the surface on which the temporary support is provided.
  • the cover film include a resin film and paper.
  • a resin film is particularly preferable from the viewpoint of strength and flexibility.
  • 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 these, a polyethylene film, a polypropylene film, and a polyethylene terephthalate film are preferable.
  • the average thickness of the cover film is not particularly limited, and preferably 1 ⁇ m to 2 mm, for example.
  • the photosensitive transfer material according to the present disclosure may have layers other than those described above (hereinafter also referred to as “other layers”).
  • other layers include a contrast enhancement layer and a thermoplastic resin layer.
  • paragraph 0134 of WO2018 / 179640 for the preferred embodiment of the thermoplastic resin layer, paragraphs 0189 to 0193 of JP 2014-85643 A, and further preferred layers. Aspects are described in paragraphs 0194 to 0196 of JP 2014-85643 A, and the contents of this publication are incorporated in this specification.
  • a photosensitive transfer material 100 shown in FIG. 1 includes a temporary support 12, a transfer layer 14 formed by stacking a photosensitive resin layer 14-1 and an intermediate layer 14-2, and a cover film 16 stacked in this order. Yes.
  • transfer layer when “transfer layer” is described in the present disclosure, it means both the laminated photosensitive resin layer and the intermediate layer.
  • the method for producing the photosensitive transfer material according to the present disclosure is not particularly limited, and a known production method such as a known method for forming each layer can be used.
  • a method for producing a photosensitive transfer material according to the present disclosure an intermediate layer forming composition is applied on a temporary support and dried to form an intermediate layer, and a photosensitive resin composition is applied to the intermediate layer.
  • a method including a step of applying and drying to form a photosensitive resin layer is preferable.
  • the manufacturing method of the photosensitive transfer material which concerns on this indication further includes the process of providing a cover film on the said photosensitive resin layer after the process of forming the said photosensitive resin layer.
  • the method for producing a resin pattern according to the present disclosure is not particularly limited as long as it is a method for producing a resin pattern using the photosensitive transfer material according to the present disclosure, but the temporary support in the photosensitive transfer material according to the present disclosure.
  • a step of bringing the outermost layer on the side having the photosensitive resin layer into contact with the substrate and bonding (hereinafter, also referred to as “bonding step”), and a step of pattern exposure of the photosensitive resin layer (hereinafter referred to as “bonding step”).
  • an “exposure process”) and a process of developing the exposed photosensitive resin layer to form a pattern hereinafter also referred to as “development process” in this order. Is preferred.
  • the substrate in the method for producing a resin pattern according to the present disclosure is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface.
  • the circuit wiring manufacturing method according to the present disclosure may be any method that uses the photosensitive transfer material according to the present disclosure, but the photosensitive resin layer according to the present disclosure has a photosensitive resin layer on the temporary support.
  • a step of bonding the outermost layer on the side having the conductive layer to a substrate having a conductive layer hereinafter sometimes referred to as a “bonding step”
  • pattern exposure of the photosensitive resin layer in the bonded photosensitive transfer material hereinafter sometimes referred to as a “bonding step”.
  • a process, a process of developing at least the photosensitive resin layer subjected to pattern exposure to form a resin pattern, and a process of etching the substrate in a region where the resin pattern is not disposed (hereinafter referred to as “etching process”). May be included in this order.
  • the substrate in the circuit wiring manufacturing method according to the present disclosure is preferably a substrate having the conductive layer on a surface thereof.
  • the manufacturing method of the circuit wiring which concerns on this indication also has the aspect which repeats several times by making the 4 processes of the said bonding process, the said exposure process, the said image development process, and the said etching process into 1 set.
  • the circuit wiring manufacturing method according to the present disclosure includes four steps of the bonding step, the exposure step, the development step, and the etching step. After that, an embodiment in which the exposure process is performed on the resin pattern, and the development process and the etching process are further performed is also preferable.
  • the photosensitive resin layer is a positive type in which a portion not irradiated with actinic rays is left as an image.
  • the positive type photosensitive resin layer by irradiating actinic rays, for example, using a photosensitizer that generates acid upon irradiation with actinic rays, the solubility of the exposed portions is increased.
  • the substrate can be reused (reworked) by overall exposure or the like.
  • International Publication No. 2006/190405 can be referred to, the contents of which are incorporated herein.
  • the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure includes 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 disclosure. It is preferable to include a step of bonding to a substrate, preferably a substrate having a conductive layer (bonding step). In the bonding step, the conductive layer is preferably pressure-bonded so that the outermost layer on the side having the photosensitive resin layer is in contact with the temporary support in the photosensitive transfer material according to the present disclosure. .
  • the patterned photosensitive resin layer after exposure and development can be suitably used as an etching resist when the conductive layer is etched.
  • a well-known transfer method and a lamination method can be used.
  • the bonding of the photosensitive transfer material to the substrate is preferably performed by stacking the outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer on the substrate, and applying pressure and heating with a roll or the like.
  • known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
  • the method for manufacturing circuit wiring according to the present disclosure is preferably performed by a roll-to-roll method.
  • substrate is a resin film.
  • the roll-to-roll method uses a substrate that can be wound and unwound as a substrate, and unwinds the substrate or a structure including the substrate before any step included in the circuit wiring manufacturing method ( And a step of winding a structure including a base material or a substrate (also referred to as a “winding step”) after any of the steps, and at least one of the steps (Preferably, all processes or all processes other than the heating process) are performed while conveying a structure including a base material or a substrate.
  • the unwinding method in the unwinding step and the winding method in the unwinding step are not particularly limited, and any known method may be used in the manufacturing method applying the roll-to-roll method.
  • the substrate used in the present disclosure is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface of a base material.
  • substrate has a conductive layer on base materials, such as glass, a silicon
  • the substrate is preferably transparent.
  • the refractive index of the substrate is preferably 1.50 to 1.52.
  • the base material may be composed of a light-transmitting base material such as a glass base material, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used.
  • materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.
  • a substrate having a small optical distortion In the case of using a resin film substrate as the substrate, it is more preferable to use a substrate having a small optical distortion and a substrate having a high transparency.
  • the material include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.
  • a film base material is preferable from the viewpoint of manufacturing by a roll-to-roll method.
  • the substrate is particularly preferably a sheet-shaped resin composition.
  • Examples of the conductive layer formed on the substrate include any conductive layer used for general circuit wiring or touch panel wiring.
  • the conductive layer is at least one 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, from the viewpoints of conductivity and fine wire formability. It is preferably mentioned, more preferably a metal layer, and particularly preferably a copper layer or a silver layer. Moreover, you may have 1 layer of conductive layers on a base material, or you may have 2 or more layers. In the case of two or more layers, it is preferable to have conductive layers of different materials. Examples of the material for the conductive layer include metals and conductive metal oxides.
  • 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 2 . “Conductivity” in the present disclosure means that the volume resistivity is less than 1 ⁇ 10 6 ⁇ cm, and the volume resistivity is preferably less than 1 ⁇ 10 4 ⁇ cm.
  • the circuit wiring manufacturing method when a substrate having a plurality of conductive layers on a base material is used, at least one of the plurality of conductive layers preferably includes a conductive metal oxide.
  • the conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition part used in a capacitive touch panel or a wiring of a peripheral extraction part.
  • the manufacturing method of the resin pattern which concerns on this indication, or the manufacturing method of the circuit wiring which concerns on this indication includes the process (exposure process) of carrying out pattern exposure of the said photosensitive resin layer after the said bonding process.
  • the detailed arrangement and specific size of the pattern are not particularly limited. Since it is desired to improve the display quality of a display device (for example, a touch panel) including an input device having a circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure and to reduce the area occupied by the extraction wiring as much as possible, At least a part (particularly the electrode pattern of the touch panel and the part of the extraction wiring) is preferably a fine line of 100 ⁇ m or less, and more preferably a fine line of 70 ⁇ m or less.
  • any light source capable of irradiating light in a wavelength region capable of exposing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.) can be appropriately selected and used.
  • a wavelength region capable of exposing the photosensitive resin layer for example, 365 nm, 405 nm, etc.
  • an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, LED (LightLEDEmitting Diode) and the like can be mentioned.
  • the exposure dose is preferably 5 mJ / cm 2 to 200 mJ / cm 2 , and more preferably 10 mJ / cm 2 to 100 mJ / cm 2 .
  • pattern exposure may be performed after the temporary support is peeled off from the photosensitive resin layer. Before the temporary support is peeled off, pattern exposure is performed through the temporary support, and then the temporary support is peeled off. May be. In order to prevent mask contamination due to contact between the photosensitive resin layer and the mask and to avoid the influence on the exposure caused by foreign matter attached to the mask, it is preferable to perform pattern exposure without peeling off the temporary support.
  • the pattern exposure may be exposure through a mask or direct exposure using a laser or the like.
  • the method of manufacturing a resin pattern according to the present disclosure or the method of manufacturing a circuit wiring according to the present disclosure includes a step of developing the exposed photosensitive resin layer to form a resin pattern after the exposing step (developing step). ) Is preferably included.
  • the photosensitive transfer material has an intermediate layer
  • the exposed intermediate layer is also removed together with the exposed photosensitive resin layer in the development step.
  • the intermediate layer in the unexposed area may also be removed in a form of being dissolved or dispersed in the developer.
  • the developer is not particularly limited as long as the non-image portion of the photosensitive resin layer can be removed.
  • a known developer such as the developer described in JP-A No. 5-72724 can be used.
  • the developing solution is preferably a developing solution in which the exposed portion (positive type) of the photosensitive resin layer has a dissolution type developing behavior.
  • an alkaline aqueous developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is preferable.
  • the developer may further contain a water-soluble organic solvent, a surfactant and the like. Examples of the developer suitably used in the present disclosure include the developer described in Paragraph 0194 of International Publication No. 2015/092731.
  • the development method is not particularly limited and may be any of paddle development, shower development, shower and spin development, dip development, and the like.
  • the shower development will be described.
  • the exposed portion can be removed by spraying the developer onto the exposed photosensitive resin layer by shower. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
  • the liquid temperature of the developer is preferably 20 ° C. to 40 ° C.
  • the post-baking process which heat-processes the pattern containing the photosensitive resin layer obtained by image development.
  • the post-baking is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably in an environment of 50.66 kPa or more. On the other hand, it is more preferable to carry out in an environment of 111.46 kPa or less, and it is particularly preferable to carry out in an environment of 101.3 kPa or less.
  • the post-baking temperature is preferably 80 ° C. to 250 ° C., more preferably 110 ° C. to 170 ° C., and particularly preferably 130 ° C. to 150 ° C.
  • the post-baking time is preferably 1 to 30 minutes, more preferably 2 to 10 minutes, and particularly preferably 2 to 4 minutes.
  • the post-bake may be performed in an air environment or a nitrogen substitution environment.
  • steps such as a post-exposure step may be provided before the etching step described later.
  • the manufacturing method of the circuit wiring which concerns on this indication includes the process (etching process) of carrying out the etching process of the board
  • the conductive layer is etched using the pattern formed from the photosensitive resin layer in the developing step as an etching resist.
  • a method for the etching treatment a known method such as a method described in paragraphs 0048 to 0054 of JP 2010-152155 A, a dry etching method such as a known plasma etching, or the like can be applied.
  • a wet etching method which is generally performed and is immersed in an etching solution can be given.
  • an etchant used for wet etching an acid type or alkaline type etchant may be appropriately selected according to an object to be etched.
  • acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and mixed aqueous solutions of acidic components and salts of ferric chloride, ammonium fluoride, potassium permanganate, etc. Is done.
  • the acidic component a component obtained by combining a plurality of acidic components may be used.
  • alkaline type etchants include aqueous solutions of alkali components such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, salts of organic amines such as tetramethylammonium hydroxide, alkaline components and potassium permanganate. Examples thereof include a mixed aqueous solution of salt.
  • alkali component a component obtained by combining a plurality of alkali components may be used.
  • the temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower.
  • the resin pattern used as an etching mask preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower. Therefore, the photosensitive resin layer is prevented from being peeled off during the etching process, and a portion where the photosensitive resin layer does not exist is selectively etched. After the etching process, in order to prevent contamination of the process line, a cleaning process for cleaning the etched substrate and a drying process for drying the cleaned substrate may be performed as necessary.
  • the manufacturing method of the circuit wiring which concerns on this indication performs the process (removal process) of removing a resin pattern.
  • the removal step is not particularly limited and can be performed as necessary, but is preferably performed after the etching step.
  • medical treatment can be mentioned, It can mention especially preferably using a removal liquid.
  • a method for removing the photosensitive resin layer the substrate having the photosensitive resin layer or the like is immersed in a removing solution that is being stirred at preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 1 to 30 minutes. A method is mentioned.
  • the removing liquid examples include inorganic alkali components such as sodium hydroxide and potassium hydroxide, or organic alkalis such as primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Examples thereof include removal solutions in which the components are dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Alternatively, the removal liquid may be used and removed by a spray method, a shower method, a paddle method, or the like.
  • inorganic alkali components such as sodium hydroxide and potassium hydroxide
  • organic alkalis such as primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. Examples thereof include removal solutions in which the components are dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.
  • the removal liquid may be used and removed by a spray method, a shower method, a paddle method
  • ⁇ Entire exposure of photosensitive resin layer It is preferable to include a step of exposing the entire surface of the photosensitive resin layer (also referred to as “overall exposure step”) before the removing step. Furthermore, if necessary, a step of heating the photosensitive resin layer exposed on the entire surface (also referred to as “heating step”) may be included.
  • the entire surface exposure step and the heating step are preferably performed after the etching step and before the removal step.
  • a well-known exposure light source can be used. From the viewpoint of removability, it is preferable to use a light source including light having the same wavelength as that in the exposure step.
  • the exposure amount in the overall exposure step is preferably 5mJ / cm 2 ⁇ 1,000mJ / cm 2, more preferably 10mJ / cm 2 ⁇ 800mJ / cm 2, 100mJ / Particularly preferred is cm 2 to 500 mJ / cm 2 .
  • the exposure amount in the overall exposure step is preferably greater than or equal to the exposure amount in the exposure step, and more preferably greater than the exposure amount in the exposure step, from the viewpoint of removability.
  • the method for manufacturing circuit wiring according to the present disclosure may include an arbitrary process (other processes) other than those described above.
  • other processes other processes
  • the exposure step, the development step, and other steps in the present disclosure the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present disclosure.
  • the method of manufacturing a resin pattern according to the present disclosure or the method of manufacturing a circuit wiring according to the present disclosure includes a step of peeling the cover film of the photosensitive transfer material when the photosensitive transfer material according to the present disclosure has a cover film. (Sometimes 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.
  • the manufacturing method of the circuit wiring which concerns on this indication can include the process of reducing the visible light reflectance of some or all of the some conductive layers on a base material.
  • the treatment for reducing the visible light reflectance include an oxidation treatment.
  • the visible light reflectance can be reduced by blackening the copper by oxidizing copper.
  • paragraphs 0017 to 0025 of JP2014-150118A and paragraphs 0041, 0042, 0048 and 0058 of JP2013-206315A are described. The contents of this publication are incorporated herein.
  • the method for manufacturing a circuit wiring preferably 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.
  • the above-described second electrode pattern can be formed while being insulated from the first electrode pattern.
  • an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.
  • a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
  • the circuit wiring manufacturing method uses a substrate having a plurality of conductive layers on both surfaces of a base material, and sequentially or simultaneously forms a circuit on the conductive layers formed on both surfaces of the base material. It is also preferable. With such a configuration, it is possible to form a circuit wiring for a touch panel in which a first conductive pattern is formed on one surface of the substrate and a second conductive pattern is formed on the other surface. Moreover, it is also preferable to form the circuit wiring for touch panels of such a structure from both surfaces of a base material by roll-to-roll.
  • the circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure can be applied to various apparatuses.
  • an input device etc. are mentioned, for example, it is preferred that it is a touch panel, and it is more preferred that it is a capacitance type touch panel.
  • the input device can be applied to a display device such as an organic EL display device or a liquid crystal display device.
  • the touch panel manufacturing method according to the present disclosure may be a method using the photosensitive transfer material according to the present disclosure, but the side having the photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to the present disclosure.
  • a step of bringing the outermost layer into contact with a substrate having a conductive layer (bonding step), a step of pattern exposing the photosensitive resin layer (exposure step), and developing the exposed photosensitive resin layer It is preferable to include a step of forming a resin pattern (developing step) and a step of etching the substrate in a region where the resin pattern is not disposed (etching step) in this order.
  • the specific aspects of each process and the embodiments such as the order of performing each process are as described in the above-mentioned section “Method of manufacturing circuit wiring”.
  • the preferred embodiment is also the same.
  • the touch panel manufacturing method according to the present disclosure can refer to a known touch panel manufacturing method except the above.
  • the manufacturing method of the touchscreen which concerns on this indication may also include arbitrary processes (other processes) other than having mentioned above.
  • FIGS. 3 and 4 An example of a mask pattern used in the touch panel manufacturing method according to the present disclosure is shown in FIGS. 3 and 4.
  • SL and G are non-image portions (light-shielding portions), and DL is a virtual alignment alignment frame.
  • the circuit wiring having the pattern A corresponding to SL and G is formed by exposing the photosensitive resin layer through the mask having the pattern A shown in FIG. Touch panel can be manufactured. Specifically, it can be produced by the method described in FIG. 1 of International Publication No. 2016/0190405.
  • G is a portion where a transparent electrode (touch panel electrode) is formed
  • SL is a portion where a wiring of a peripheral extraction portion is formed.
  • the touch panel according to the present disclosure is a touch panel having at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure.
  • the touch panel according to the present disclosure preferably includes at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
  • a detection method in the touch panel according to the present disclosure any known method such as a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Among these, the electrostatic capacity method is preferable.
  • the touch panel type a so-called in-cell type (for example, those described in FIGS.
  • JP 2013-168125 A a so-called on-cell type
  • OGS One Glass Solution
  • TOL Touch-on-Lens
  • other configurations for example, those shown in FIG. 6 of JP2013-164671A
  • various out-cell types for example, GG, G1, G2, GFF, GF2, GF1, G1F, etc.
  • Examples of the touch panel according to the present disclosure include those described in paragraph 0229 of JP-A-2017-120345.
  • Example and comparative example in the first embodiment of the photosensitive transfer material according to the present disclosure The abbreviation regarding the component used in the Example represents the following compounds, respectively.
  • -Intermediate layer- [Polymer (Binder polymer for intermediate layer)]
  • Polymer B-11 Nissan HPC-SSL (Hydroxypropylcellulose Nippon Soda Co., Ltd.)
  • Polymer B-12 Metroz 60SH-03 (hydroxypropylmethylcellulose, manufactured by Shin-Etsu Chemical Co., Ltd.) [Dye]
  • A-1 Bromophenol blue (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., maximum absorption wavelength: 606 nm, water-soluble)
  • A-2 Bromocresol green (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., maximum absorption wavelength: 626 nm, water-soluble)
  • A-3 VPB-NAPS (Victoria Pure Blue naphthalene
  • A-1 Color development (that is, maximum absorption wavelength) changed at pH 4.0 or higher.
  • A-2 Color development (that is, maximum absorption wavelength) changed at pH 5.4 or higher.
  • A-3 Even when the pH was changed at pH 1 to 14, the color development (that is, the maximum absorption wavelength) did not change.
  • G-1 0.1N sodium hydroxide aqueous solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
  • G-2 0.1N aqueous potassium hydroxide solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
  • G-3 0.1N lithium hydroxide aqueous solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
  • G-4 Tetrabutylammonium hydroxide (40% by mass aqueous solution) (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
  • G-5 Hexadecyltrimethylammonium hydroxide (10% by mass aqueous solution) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • G-6 Choline (50% by mass aqueous solution) (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • G-7 benzyltrimethylam
  • ATHF 2-tetrahydrofuranyl acrylate (synthetic product)
  • MATHF 2-tetrahydrofuranyl methacrylate (synthetic product)
  • ATHP Tetrahydro-2H-pyran-2-yl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • MATHP Tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • MAEVE 1-ethoxyethyl methacrylate (Fuji Film Wako Pure Chemical Industries, Ltd.) TBMA: t-butyl methacrylate (Fuji Film Wako Pure Chemical Industries, Ltd.)
  • AA Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • MAA Methacrylic acid (manufactured
  • C-4 CPI-310TS (triarylsulfonium salt, manufactured by San Apro Co., Ltd.)
  • D-2 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • D-3 1,5-diazabicyclo [4.3.0] -5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • E-1 F-552 (fluorine nonionic surfactant, manufactured by DIC Corporation)
  • E-2 F-554 (Fluorine nonionic surfactant, manufactured by DIC Corporation)
  • Example 1 Preparation of intermediate layer composition 1> The following components were mixed and filtered with a polytetrafluoroethylene filter having a pore size of 5.0 ⁇ m to prepare an intermediate layer composition 1.
  • ⁇ Preparation of resist layer composition 1> The following components were mixed and filtered through a polytetrafluoroethylene filter having a pore size of 1.0 ⁇ m to prepare a resist layer composition 1.
  • MEK methyl ethyl ketone: manufactured by Maruzen Petrochemical Co., Ltd.
  • 306.0 parts by mass Normal propyl acetate manufactured by Showa Denko KK
  • 459.9 parts by mass Polymer B-1 solution 423.5 parts by mass
  • Photoacid generation Agent C-1: 9.00 parts by mass Basic compound
  • An intermediate layer composition 1 is formed on a polyethylene terephthalate film (hereinafter also referred to as “PET (A)”) having a thickness of 16 ⁇ m, which is a temporary support, with a dry film thickness of 1.8 ⁇ m using a slit nozzle.
  • PET (A) polyethylene terephthalate film
  • the resist layer composition 1 was applied in an amount such that the dry film thickness was 3.0 ⁇ m using a slit nozzle.
  • a polypropylene film manufactured by Oji F-Tex Co., Ltd., Alphan PK-002 was pressure-bonded as a cover film to prepare a photosensitive transfer material.
  • the intermediate layer compositions 2 to 18 were prepared by dissolving and mixing with a filter of polytetrafluoroethylene having a pore size of 1.0 ⁇ m. Further, as shown in Table 3, 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 a photoacid generator C-4 was further added.
  • the polymer, photoacid generator, basic compound, surfactant, and other components are mixed solvents of n-propyl acetate and methyl ethyl ketone so that the solid content ratio (mass ratio) shown in Table 4 below is obtained.
  • the following component was mixed and the resist layer composition 11 was prepared by filtering with the filter made from a polytetrafluoroethylene with a hole diameter of 1.0 micrometer.
  • Example 1 except that the intermediate layer composition 1 was replaced with the intermediate layer compositions 2 to 19 and the resist layer composition 1 was replaced with the resist layer compositions 2 to 11, respectively. In the same manner, a photosensitive transfer material was produced.
  • Comparative Example 1 In Example 1, the intermediate layer composition 1 was replaced with the comparative intermediate layer composition 1 prepared without adding the dye A-1 and the pH adjuster G-1 used for the preparation of the intermediate layer composition 1.
  • a photosensitive transfer material of Comparative Example 1 was produced in the same manner as Example 1 except for the above.
  • 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 comparative intermediate layer composition 2.
  • Example 201 instead of the intermediate layer composition 19, as shown in Table 3, it was prepared without adding the dye A-1 and the photoacid generator C-4 used for the preparation of the intermediate layer composition 19.
  • a photosensitive transfer material was produced in the same manner as in Example 201 except that the comparative intermediate layer composition 3 was used.
  • the produced photosensitive transfer material was subjected to a roll temperature of 90 ° C., a linear pressure of 0.8 MPa, and a linear velocity of 3.0 m / min. It laminated on the PET board
  • the temporary support of the photosensitive transfer material is contacted with a glass mask having a line-and-space pattern (duty ratio of 1: 1) having a line width of 10 ⁇ m without peeling off the temporary support, and ultrahigh pressure is passed through the mask.
  • the resist layer was exposed with an exposure dose of 200 mJ / cm 2 with a mercury lamp. After leaving for 4 hours, the exposed line and space pattern was observed with an optical microscope and evaluated according to the following evaluation criteria.
  • 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 have the configuration shown in Table 6 below.
  • a PET substrate with a copper layer in which a copper layer was formed by a sputtering method at a thickness of 200 nm on a polyethylene terephthalate (PET) film having a thickness of 100 ⁇ m was used.
  • the produced photosensitive transfer material was cut into a size of 50 cm ⁇ 50 cm to obtain a sample piece, and the cover film of the obtained sample piece was peeled off, and the roll temperature was 90 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 4.0 m / min.
  • the film was laminated on a PET film with a copper layer under the following laminating conditions.
  • Example 101 Indium tin oxide (ITO) was deposited as a second conductive layer on a 100 ⁇ m thick PET substrate by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer by vacuum deposition. A film was formed with a thickness of 200 nm to obtain a circuit formation substrate.
  • the photosensitive transfer material 1 obtained in Example 1 was laminated on the copper layer (linear pressure 0.8 MPa, linear velocity 3.0 m / min, roll temperature 90 ° C.). Contact pattern exposure was performed using a photomask provided with a pattern shown in FIG.
  • pattern A having a configuration in which conductive layer pads are connected in one direction without peeling off the temporary support.
  • the solid line portion SL and the gray portion G are light shielding portions, and the dotted line portion DL virtually shows an alignment alignment frame. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A.
  • the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), A substrate on which copper (solid line portion SL) and ITO (gray portion G) were both drawn with the pattern A was obtained.
  • pattern alignment was performed using a photomask provided with openings of the pattern shown in FIG. 4 (hereinafter also referred to as “pattern B”) in the aligned state, and development and washing were performed.
  • the gray portion G is a light shielding portion
  • the dotted line portion DL is a virtual alignment alignment frame.
  • the copper layer was etched using Cu-02, and the remaining resist layer was stripped using a stripping solution (10 mass% sodium hydroxide aqueous solution) to obtain a circuit wiring board. As a result, a circuit wiring board was obtained. When observed with a microscope, there was no peeling or chipping, and the pattern was clean.
  • Example 102 On a 100 ⁇ m-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer by vacuum deposition at a thickness of 200 nm. The film was formed into a circuit forming substrate.
  • the photosensitive transfer material 1 obtained in Example 1 was laminated on the copper layer (linear pressure 0.8 MPa, linear velocity 3.0 m / min, roll temperature 90 ° C.).
  • the resist layer was subjected to pattern exposure using a photomask provided with a pattern A shown in FIG. 3 having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A.
  • the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), A substrate on which copper (solid line portion SL) and ITO (gray portion G) were both drawn with the pattern A was obtained.
  • PET (A) was laminated as a protective layer on the remaining resist.
  • pattern alignment was performed using a photomask provided with an opening of the pattern B shown in FIG. 4 in the aligned state, and after developing the PET (A), development and washing were performed. Thereafter, the copper wiring was etched using Cu-02, and the remaining resist layer was stripped using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
  • a stripping solution KP-301 manufactured by Kanto Chemical Co., Inc.
  • the weight average molecular weights of the polymers A-1 to A-6 were 20,000, respectively.
  • ⁇ Photo acid generator> B-1 Compound having the structure shown below (Compound described in paragraph 0227 of JP 2013-47765 A, synthesized according to the method described in paragraph 0227)
  • the unit of the amount of each component in Table 8 is part by mass.
  • An intermediate layer forming composition 1 was prepared according to the following formulation.
  • composition 1 for Forming Intermediate Layer The composition shown in the following was dissolved and mixed to obtain an intermediate layer forming composition 1.
  • HPC Hydroxypropyl cellulose
  • HPC-SSL Hydroxypropyl cellulose
  • HMPC Hydroxypropyl methylcellulose
  • TC-5 Hydroxypropyl methylcellulose
  • Snowtex O Silica particles, manufactured by Nissan Chemical Industries, arithmetic average particle size 12 nm, surface state anionic (silanol) Snowtex XS: Silica particles, manufactured by Nissan Chemical Industries, arithmetic average particle size 5 nm, surface state anionic (silanol) Snowtex OS: Silica particles, manufactured by Nissan Chemical Industries, arithmetic average particle size 9 nm, surface state anionic (silanol) Snowtex O-40: Silica particles, manufactured by Nissan Chemical Industries, arithmetic average particle size 22 nm, surface state anionic (silanol) Snowtex OL: Silica particles, manufactured by Nissan Chemical Industries, arithmetic average particle size 22 nm, surface state anionic (silanol) Snowtex OL: Silica particles, manufactured
  • Example 2-1 ⁇ Production of photosensitive transfer material>
  • the composition for forming an intermediate layer 1 is formed on a polyethylene terephthalate film having a thickness of 30 ⁇ m serving as a temporary support so that the composition shown in Table 10 below is applied.
  • the film was applied to a thickness of 8 ⁇ m and passed through a drying zone at 100 ° C. over 40 seconds to form an intermediate layer.
  • the photosensitive resin composition A-1 was applied onto the intermediate layer using a slit nozzle so that the coating width was 1.0 m and the film thickness was 3 ⁇ m, and a 100 ° C. drying zone was applied for 40 seconds.
  • the photosensitive resin layer was formed by passing through.
  • a polyethylene film (Tradeger's OSM-N) is pressure-bonded as a cover film (protective film) on the photosensitive resin layer to produce a photosensitive transfer material 2-1, and the photosensitive transfer material 2-1 is wound up. In roll form.
  • Photosensitive transfer materials 2-2 to 2-27 were prepared in the same manner as in Example 2-1, except that the compositions shown in Table 10 below were used.
  • Photosensitive transfer materials 2-C1 to 2-C4 were prepared in the same manner as in Example 2-1, except that the compositions shown in Table 10 below were used.
  • Photosensitive transfer material 2 was prepared in the same manner as in Example 2-1, except that the composition shown in Table 11 below was used to form a water-soluble resin layer, and then an intermediate layer was formed in the same manner as the water-soluble resin layer. -28 to 2-32 were produced.
  • the formation of the water-soluble resin layer used the composition of Table 11 among the compositions for intermediate
  • the layer was composed of 4 layers: (layer) / particle, layer containing the above polar compound and water-soluble resin (intermediate layer) / photosensitive resin layer. Further, when the cross sections of the obtained photosensitive transfer materials of Examples 2-28 to 2-32 were observed using the SIMS method, it was found that any of the above polar compounds was contained in the intermediate layer. It was.
  • a PET substrate with a copper layer was used in which a copper film was formed to a thickness of 200 nm by a vacuum deposition method on a polyethylene terephthalate (PET) film having a thickness of 100 ⁇ m.
  • PET polyethylene terephthalate
  • the cover film was peeled from the photosensitive transfer material of Example 2-1, and the photosensitive transfer material obtained on the copper layer in the above-mentioned PET substrate with a copper layer was transferred at 100 ° C., a speed of 4 m / min, and a linear pressure of 0.6 MPa. After laminating under the above conditions, the temporary support was peeled off to produce a laminate in which a positive photosensitive layer was laminated on the copper layer.
  • the initial filtration pressure is 0.1 MPa or less, and the filtration pressure change when 10 L is filtered is 0.01 MPa or more and less than 0.05 MPa.
  • the initial filtration pressure is a value exceeding 0.1 MPa, or the filtration pressure change after 10 L filtration is 0.05 MPa or more.
  • the photosensitive transfer materials of the examples are superior in adhesion between the intermediate layer and the photosensitive resin layer as compared with the photosensitive transfer materials of the comparative examples.
  • Table 11 it can be seen from Table 11 that by further producing a water-soluble resin layer, the adhesion between the intermediate layer and the photosensitive resin layer, storage stability, and liquid stability are all excellent.
  • the photosensitive transfer material or the intermediate layer forming composition can be used without being stored for a long time from the time of preparation, and there is no practical problem. Can be used.
  • Example 2-101 On the 100 ⁇ m-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer at a thickness of 200 nm by vacuum evaporation. Thus, a circuit forming substrate was obtained.
  • the photosensitive transfer material obtained in Example 2-1 on the copper layer was peeled off the protective film and bonded to the substrate (lamination roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.), a laminate. The obtained laminate was exposed to a contact pattern using a photomask provided with a pattern A shown in FIG.
  • Example 3 having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support.
  • a high pressure mercury lamp having i-line (365 nm) as an exposure dominant wavelength was used for the exposure.
  • the temporary support was peeled off, developed and washed with water to obtain a pattern A.
  • the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), A substrate on which both copper and ITO were drawn in pattern A was obtained.
  • a temporary support similar to that in Example 2-1 was laminated as a protective layer on the remaining resist.
  • Example 2-102 In the same manner as in Example 2-101, after obtaining the substrate drawn with pattern A, the protective transfer film was peeled off the photosensitive transfer material obtained in Example 1 on the remaining resist, Bonding was again performed under the same conditions as in Example 2-101. With the alignment aligned, pattern exposure is performed using a photomask provided with an opening of pattern B without peeling off the temporary support, and then the temporary support is peeled off, followed by development and washing to obtain pattern B. It was. Next, the copper wiring was etched under the same conditions as in Example 2-101, and the remaining photosensitive resin layer was peeled off to obtain a circuit wiring board having a conductive pattern. When the obtained circuit wiring board was observed with a microscope, it was a clean pattern with no peeling or chipping.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Human Computer Interaction (AREA)
  • Materials For Photolithography (AREA)

Abstract

La présente invention concerne un matériau de transfert photosensible ayant, dans l'ordre indiqué, un corps de support temporaire, une couche intermédiaire et une couche de réserve, la couche intermédiaire contenant un composant (A) qui est un pigment ayant une longueur d'onde d'absorption maximale de 450 nm ou plus dans la plage de longueur d'onde de 400-780 nm lorsque la couleur est produite, la longueur d'onde d'absorption maximale variant selon qu'un acide, une base ou un radical est impliqué ; un procédé de fabrication de câblage de circuit ; et un procédé de fabrication d'un écran tactile.
PCT/JP2019/004043 2018-02-05 2019-02-05 Matériau de transfert photosensible, procédé de fabrication de câblage de circuit, et procédé de fabrication d'écran tactile WO2019151534A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201980011644.1A CN111684359A (zh) 2018-02-05 2019-02-05 感光性转印材料、电路布线的制造方法及触摸面板的制造方法

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2018-018478 2018-02-05
JP2018018478 2018-02-05
JP2018098329 2018-05-22
JP2018-098329 2018-05-22
JP2018162138A JP6832899B2 (ja) 2018-02-05 2018-08-30 感光性転写材料、回路配線の製造方法、及び、タッチパネルの製造方法
JP2018-162138 2018-08-30
JP2019-016912 2019-02-01
JP2019016912A JP7007308B2 (ja) 2019-02-01 2019-02-01 感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法

Publications (1)

Publication Number Publication Date
WO2019151534A1 true WO2019151534A1 (fr) 2019-08-08

Family

ID=67478347

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/004043 WO2019151534A1 (fr) 2018-02-05 2019-02-05 Matériau de transfert photosensible, procédé de fabrication de câblage de circuit, et procédé de fabrication d'écran tactile

Country Status (1)

Country Link
WO (1) WO2019151534A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021225162A1 (fr) * 2020-05-07 2021-11-11 富士フイルム株式会社 Film de transfert, procédé de fabrication de stratifié, capteur tactile et procédé de fabrication d'une carte de circuit imprimé

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002099078A (ja) * 2000-09-25 2002-04-05 Nippon Columbia Co Ltd マスタリング原盤
JP2004205732A (ja) * 2002-12-25 2004-07-22 Fuji Photo Film Co Ltd カラーフィルターの製造方法
JP2006085116A (ja) * 2004-08-17 2006-03-30 Fuji Photo Film Co Ltd 感光性転写材料並びにパターン形成方法及びパターン
JP2006205397A (ja) * 2005-01-25 2006-08-10 Fuji Photo Film Co Ltd 機上現像型平版印刷版原版及びそれを用いた平版印刷方法
JP2006243546A (ja) * 2005-03-04 2006-09-14 Fuji Photo Film Co Ltd パターン形成材料、並びにパターン形成装置及びパターン形成方法
WO2018008376A1 (fr) * 2016-07-06 2018-01-11 富士フイルム株式会社 Composition photosensible, film de transfert, film durci, panneau tactile et procédé de fabrication de panneau tactile

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002099078A (ja) * 2000-09-25 2002-04-05 Nippon Columbia Co Ltd マスタリング原盤
JP2004205732A (ja) * 2002-12-25 2004-07-22 Fuji Photo Film Co Ltd カラーフィルターの製造方法
JP2006085116A (ja) * 2004-08-17 2006-03-30 Fuji Photo Film Co Ltd 感光性転写材料並びにパターン形成方法及びパターン
JP2006205397A (ja) * 2005-01-25 2006-08-10 Fuji Photo Film Co Ltd 機上現像型平版印刷版原版及びそれを用いた平版印刷方法
JP2006243546A (ja) * 2005-03-04 2006-09-14 Fuji Photo Film Co Ltd パターン形成材料、並びにパターン形成装置及びパターン形成方法
WO2018008376A1 (fr) * 2016-07-06 2018-01-11 富士フイルム株式会社 Composition photosensible, film de transfert, film durci, panneau tactile et procédé de fabrication de panneau tactile

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021225162A1 (fr) * 2020-05-07 2021-11-11 富士フイルム株式会社 Film de transfert, procédé de fabrication de stratifié, capteur tactile et procédé de fabrication d'une carte de circuit imprimé

Similar Documents

Publication Publication Date Title
JP6999693B2 (ja) 感光性転写材料、樹脂パターン製造方法、及び、配線製造方法
WO2020105457A1 (fr) Matériau de transfert, procédé de production de motif de résine, procédé de production de câblage de circuit et procédé de production d'écran tactile
JP6995865B2 (ja) 感光性転写材料の製造方法、及び、回路配線の製造方法
JP2019191518A (ja) 感光性転写材料、レジストパターンの製造方法、回路配線の製造方法
JP2022069472A (ja) 感光性転写材料及びその製造方法、樹脂パターンの製造方法、並びに、回路配線の製造方法
JPWO2020066351A1 (ja) パターン付き基材の製造方法、回路基板の製造方法及びタッチパネルの製造方法
JPWO2019065113A1 (ja) 回路配線の製造方法及びタッチパネルの製造方法
JP6812556B2 (ja) 感光性樹脂組成物、感光性転写材料、回路配線の製造方法、及び、タッチパネルの製造方法
JP7007308B2 (ja) 感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法
JP6992097B2 (ja) レジストパターンの製造方法、回路基板の製造方法及びタッチパネルの製造方法
WO2019151534A1 (fr) Matériau de transfert photosensible, procédé de fabrication de câblage de circuit, et procédé de fabrication d'écran tactile
JP6832899B2 (ja) 感光性転写材料、回路配線の製造方法、及び、タッチパネルの製造方法
JP6968273B2 (ja) 感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法
JP6808045B2 (ja) 感光性樹脂組成物、感光性転写材料、回路配線の製造方法、及び、タッチパネルの製造方法
JP7220641B2 (ja) パターン形成方法、回路基板の製造方法、電子デバイス、転写材料、及び積層体
JP7102517B2 (ja) 感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法
WO2023090253A1 (fr) Stratifié, son procédé de production et dispositif électronique
JP7048332B2 (ja) 感光性転写材料及びその製造方法、樹脂パターンの製造方法、並びに、回路配線の製造方法
TW201938384A (zh) 感光性轉印材料、電路配線之製造方法及觸控面板之製造方法
JP7011046B2 (ja) 感光性転写材料、レジストパターンの製造方法、回路配線の製造方法、タッチパネル、及び、タッチパネル表示装置
WO2019225363A1 (fr) Matériau de transfert photosensible, procédé de production de motif de résine, procédé de fabrication de câblage de circuit, et procédé de fabrication de panneau tactile
TW202112856A (zh) 感光性轉印構件、樹脂圖案之製造方法、電路配線之製造方法、觸控面板之製造方法
JP2023076241A (ja) 感光性組成物、積層体、パターン形成方法、及び、パターン付き積層体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19748253

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19748253

Country of ref document: EP

Kind code of ref document: A1