CN113056373A - Transfer material, method for manufacturing resin pattern, method for manufacturing circuit wiring, and method for manufacturing touch panel - Google Patents

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

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CN113056373A
CN113056373A CN201980075793.4A CN201980075793A CN113056373A CN 113056373 A CN113056373 A CN 113056373A CN 201980075793 A CN201980075793 A CN 201980075793A CN 113056373 A CN113056373 A CN 113056373A
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group
photosensitive resin
layer
transfer material
pattern
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海鉾洋行
藤本进二
两角一真
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Fujifilm Corp
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/02Halogenated hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • C08L101/12Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/039Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20Exposure; Apparatus therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/40Treatment after imagewise removal, e.g. baking
    • GPHYSICS
    • G06COMPUTING; CALCULATING OR COUNTING
    • G06FELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00Input 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
    • G06F3/01Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Theoretical Computer Science (AREA)
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  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A transfer material comprising a temporary support, an intermediate layer comprising a water-soluble resin, and a positive photosensitive resin layer in this order, wherein the intermediate layer comprises a surfactant having fluorine atoms, and a method for producing a resin pattern, a method for producing a circuit wiring, and a method for producing a touch panel, each using the transfer material.

Description

Transfer material, method for manufacturing resin pattern, method for manufacturing circuit wiring, and method for manufacturing touch panel
Technical Field
The present invention relates to a transfer material, a method for manufacturing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel.
Background
In a display device (such as an organic Electroluminescence (EL) display device and a liquid crystal display device) including a touch panel such as a capacitive input device, a conductive layer pattern corresponding to an electrode pattern of a sensor of a visual recognition unit, a peripheral wiring portion, and a wiring of a lead wiring portion is provided inside the touch panel.
In general, in the formation of a patterned layer, since the number of steps for obtaining a desired pattern shape is small, a method of exposing a layer of a photosensitive resin composition provided on an arbitrary substrate through a mask having a desired pattern by using a photosensitive transfer material and then developing the layer is widely used.
As a conventional photosensitive resin composition or transfer material, a material described in patent document 1 or 2 is known.
Patent document 1 describes a photosensitive transfer material comprising a temporary support, an intermediate layer, and a photosensitive resin composition layer in this order, the photosensitive resin composition layer containing a polymer having a structural unit containing an acid group protected by an acid-decomposable group and a photoacid generator, the intermediate layer being water-soluble or alkali-soluble and containing a resin C containing a structural unit containing an alcoholic hydroxyl group that is not directly bonded to a phenolic hydroxyl group or a main chain.
Patent document 2 describes a transfer laminate having at least one transfer layer on a temporary support, wherein the maximum value of the peeling force when peeling off the temporary support is 0.98 to 5.39mN/cm in a 180 ° peeling method.
Prior art documents
Patent document
Patent document 1: international publication No. 2018/179640
Patent document 2: japanese laid-open patent publication No. 2009-073022
Disclosure of Invention
Technical problem to be solved by the invention
An object of one embodiment of the present invention is to provide a transfer material having a transfer surface with few streaks.
Another object of another embodiment of the present invention is to provide a method for manufacturing a resin pattern using the transfer material, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel.
Means for solving the technical problem
The means for solving the above problem include the following means.
<1> a transfer material comprising a temporary support, an intermediate layer comprising a water-soluble resin, and a positive photosensitive resin layer in this order, wherein the intermediate layer comprises a surfactant having fluorine atoms.
<2> the transfer material according to <1>, wherein the surfactant contains a compound having a molecular weight of 700 or more.
<3> the transfer material according to <1> or <2>, wherein the surfactant has a solubility of 1g or more with respect to 100g of water at 25 ℃.
<4> the transfer material according to any one of <1> to <3>, wherein the content of the surfactant is 0.1% by mass to 1.0% by mass with respect to the total mass of the intermediate layer.
<5> the transfer material according to any one of <1> to <4>, wherein the surfactant is a surfactant having a fluoroalkyl group and an alkyleneoxy group.
<6> the transfer material according to any one of <1> to <5>, wherein the surfactant is a surfactant having a perfluoroalkyl group and a polyalkyleneoxy group.
<7> the transfer material according to any one of <1> to <6>, wherein a content of the polymer component in the positive photosensitive resin layer is 75% by mass or more with respect to a total mass of the positive photosensitive resin layer.
<8> the transfer material according to any one of <1> to <7>, wherein the positive photosensitive resin layer contains a polymer containing a structural unit having an acid group protected by an acid-decomposable group and a photoacid generator.
<9> the transfer material according to <8>, wherein the structural unit having the acid group protected by the acid-decomposable group is a structural unit represented by any one of the following formulae A1 to A3.
[ chemical formula 1]
Figure BDA0003069266620000031
In the formula A1, R11And R12Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R11And R12Any of which is alkyl or aryl, R13Represents alkyl or aryl, R11Or R12And R13May be linked to form a cyclic ether, R14Represents a hydrogen atom or a methyl group, X1Represents a single bond or a divalent linking group, R15Represents a substituent, and n represents an integer of 0 to 4.
In the formula A2, R21And R22Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R21And R22Any of which is alkyl or aryl, R23Represents alkyl or aryl, R21Or R22And R23May be linked to form a cyclic ether, R24Each independently represents a hydroxyl group, a halogen atom, an alkyl groupAlkoxy, alkenyl, aryl, aralkyl, alkoxycarbonyl, hydroxyalkyl, arylcarbonyl, aryloxycarbonyl, or cycloalkyl, and m represents an integer of 0 to 3.
In the formula A3, R31And R32Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R31And R32Any of which is alkyl or aryl, R33Represents alkyl or aryl, R31Or R32And R33May be linked to form a cyclic ether, R34Represents a hydrogen atom or a methyl group, X0Represents a single bond or a divalent linking group.
<10> a method for manufacturing a resin pattern, comprising in sequence: a step of bringing an outermost layer on a side having a positive photosensitive resin layer with respect to the temporary support in the transfer material according to any one of <1> to <9> into contact with a substrate and bonding the outermost layer to the substrate; a step of pattern-exposing the positive photosensitive resin layer; and a step of forming a resin pattern by developing the exposed positive photosensitive resin layer.
<11> a method for manufacturing a circuit wiring, comprising in order: a step of bringing an outermost layer on a side having the positive photosensitive resin layer with respect to the temporary support in the transfer material according to any one of <1> to <9> into contact with a substrate having a conductive layer and bonding the outermost layer to the substrate; a step of pattern-exposing the positive photosensitive resin layer; a step of forming a resin pattern by developing the exposed positive photosensitive resin layer; and a step of etching the conductive layer in a region where the resin pattern is not arranged.
<12> a method for manufacturing a touch panel, comprising in order: a step of bringing an outermost layer on a side having the positive photosensitive resin layer with respect to the temporary support in the transfer material according to any one of <1> to <9> into contact with a substrate having a conductive layer and bonding the outermost layer to the substrate; a step of pattern-exposing the positive photosensitive resin layer; a step of forming a resin pattern by developing the exposed positive photosensitive resin layer; and a step of etching the conductive layer in a region where the resin pattern is not disposed.
Effects of the invention
According to an embodiment of the present invention, a transfer material with less streaks on a surface to be transferred can be provided.
Further, according to another embodiment of the present invention, a method for manufacturing a resin pattern using the transfer material, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel can be provided.
Drawings
Fig. 1 is a schematic view showing an example of the layer structure of the transfer material according to the present invention.
Fig. 2 is a schematic view showing the pattern a.
Fig. 3 is a schematic view showing the pattern B.
Detailed Description
The present invention will be described below. Note that, although the description is made with reference to the drawings, the reference numerals are sometimes omitted.
In the present specification, the numerical range expressed by the term "to" means a range in which the numerical values before and after the term "to" are included as the lower limit value and the upper limit value.
In the present specification, "(meth) acrylic acid" represents both or either of acrylic acid and methacrylic acid, and "(meth) acrylate" represents both or either of acrylate and methacrylate.
In the present specification, the amount of each component in the composition refers to the total amount of a plurality of substances corresponding to each component in the composition unless otherwise specified.
In the present specification, the term "step" is not limited to an independent step, and is also included in the term as long as the desired purpose of the step is achieved even when the step cannot be clearly distinguished from other steps.
In the labeling of the group (atomic group) in the present specification, the label which is not substituted and unsubstituted includes a group having no substituent and a group having a substituent. For example, "alkyl" means to include not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, in the present specification, "exposure" includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam. The light used for exposure may be, for example, an active ray (active energy ray) such as a bright line spectrum of a mercury lamp, a far ultraviolet ray typified by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, or an electron beam.
The chemical structural formula in this specification may be described as a simplified structural formula in which a hydrogen atom is omitted.
In the present invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.
In the present invention, a combination of two or more preferred embodiments is a more preferred embodiment.
Unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are the following molecular weights: the Gel Permeation Chromatography (GPC) analysis apparatus using a column of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (each trade name manufactured by TOSOH CORPORATION) was used to perform detection using a solvent THF (tetrahydrofuran) and a differential refractometer, and polystyrene was used as a standard substance for conversion.
(transfer Material)
The transfer material (also referred to as "photosensitive transfer material") according to the present invention includes a temporary support, an intermediate layer containing a water-soluble resin, and a positive photosensitive resin layer (hereinafter, also referred to simply as "photosensitive resin layer") in this order, and the intermediate layer contains a surfactant having a fluorine atom.
The transfer material according to the present invention is a positive photosensitive transfer material.
The present inventors have found that when an intermediate layer and a positive photosensitive resin layer are produced, the positive photosensitive resin layer is a hard layer containing a resin as a main component and has low fluidity, and therefore, when the positive photosensitive resin layer is formed, the shape defects such as streaks generated at the time of forming the intermediate layer reflect the same shape defects in the positive photosensitive resin layer due to the influence of the shape of the intermediate layer, and further, when another layer on the positive photosensitive resin layer is further formed, the same shape defects may be reflected even in the layer, and thus, there is a problem that streaks are generated on the surface to be transferred in a transfer material having the intermediate layer and the positive photosensitive resin layer.
On the other hand, the negative photosensitive resin layer described in patent document 2 and the like is a layer containing a polymerizable compound and has high fluidity, and therefore, when the negative photosensitive resin layer is formed, the negative photosensitive resin layer is planarized without reflecting the influence of shape defects such as streaks generated at the time of forming the intermediate layer, and therefore, as described above, the problem of generation of streaks on the surface to be transferred does not occur.
Therefore, the problem of reducing the streaks on the transferred surface is a problem specific to the positive photosensitive resin layer.
The "transferred surface" is also referred to as a "transfer surface", and is, for example, a surface on the positive photosensitive resin layer side of a transfer material as long as the transfer material includes a temporary support, an intermediate layer, and a positive photosensitive resin layer in this order.
As a result of intensive studies, the present inventors have found that a transfer material having the above-described structure can provide a transfer material with less streaks on the surface to be transferred.
The expression mechanism of the detailed effect is not clear, but it is presumed that by having a temporary support, an intermediate layer and a positive photosensitive resin layer in this order, the intermediate layer containing a surfactant having a fluorine atom, the occurrence of streaks on the surface of the intermediate layer is suppressed, and the deterioration of the surface shape of the positive photosensitive resin layer accompanying the occurrence of streaks is suppressed, whereby a transfer material having few streaks on the surface to be transferred can be obtained.
It is assumed that the occurrence of the streaks is caused by convection of the intermediate layer-forming layer composition during the formation of the intermediate layer and by uneven volatilization of the solvent contained in the intermediate layer-forming layer composition.
Further, as described above, since the positive photosensitive resin layer is a hard layer mainly composed of a resin and has low fluidity, the influence of the streaks generated in the intermediate layer is reflected on the transfer surface and streaks are generated. The intermediate layer contains a surfactant having a fluorine atom, whereby the occurrence of the streak can be suppressed. Since the occurrence of the streaks is suppressed, it is possible to suppress the entry of air bubbles into the streaks at the adhering portion of the transfer surface at the time of transfer, and the transfer surface has excellent adhesion, and when the transfer material is used as an etching resist, there are few defects in the shape of the resin pattern derived from the streaks and air bubbles and defects accompanying the above such as disconnection of the wiring as an etching pattern, unnecessary bonding, contact (short circuit), and the like.
Therefore, the transfer material according to the present invention has the above-described configuration, and thus, the transfer material is excellent in adhesion during transfer and has fewer wiring defects when the transfer material is used as an etching resist.
The transfer material according to the present invention will be described in detail below.
< intermediate layer >
The transfer material according to the present invention has an intermediate layer.
The intermediate layer contains a surfactant having a fluorine atom and a water-soluble resin, and preferably contains a surfactant having a fluorine atom, a water-soluble resin, and a dye described later.
[ surfactant having fluorine atom ]
The intermediate layer contains a surfactant having a fluorine atom.
The surfactant having a fluorine atom may, for example, be a compound containing a group having a fluorine atom and a hydrophilic group.
The surfactant having a fluorine atom may have one or two or more groups having a fluorine atom.
The surfactant having a fluorine atom may have only one hydrophilic group or two or more hydrophilic groups.
From the viewpoint of suppressing the occurrence of streaks, the surfactant having a fluorine atom preferably has a fluoroalkyl group or a fluoroaryl group as the group having a fluorine atom, more preferably has a fluoroalkyl group, and particularly preferably has a perfluoroalkyl group.
The perfluoroalkyl group is preferably a perfluoroalkyl group having 4 or more carbon atoms, more preferably a perfluoroalkyl group having 4 to 18 carbon atoms, still more preferably a perfluoroalkyl group having 4 to 12 carbon atoms, and particularly preferably a perfluoroalkyl group having 4 to 6 carbon atoms, from the viewpoint of suppressing the occurrence of streaks.
From the viewpoint of suppressing the occurrence of streaks and the adhesion on the transfer surface at the time of transfer, the surfactant having a fluorine atom is preferably an ionic surfactant having a fluorine atom or a nonionic surfactant having a fluorine atom, more preferably an anionic surfactant having a fluorine atom or a nonionic surfactant having a fluorine atom, and particularly preferably a nonionic surfactant having a fluorine atom.
The ionic hydrophilic group is preferably an acid group, more preferably a carboxyl group, a sulfo group, a phosphonic acid group or a phosphoric acid group, and particularly preferably a phosphoric acid group, from the viewpoints of hydrophilicity, suppression of occurrence of streaks, and adhesion to the transfer surface at the time of transfer.
The nonionic hydrophilic group is preferably an alkyleneoxy group or a hydroxyl group, more preferably an alkyleneoxy group, and particularly preferably a polyalkyleneoxy group, from the viewpoints of hydrophilicity, suppression of occurrence of streaks, and adhesion to the transfer surface at the time of transfer.
From the viewpoint of suppressing the occurrence of streaks and the adhesion on the transfer surface at the time of transfer, the surfactant having a fluorine atom preferably has at least one group selected from the group consisting of an acid group and an alkyleneoxy group, more preferably has an alkyleneoxy group, and particularly preferably has a polyalkyleneoxy group as a hydrophilic group.
The above-mentioned alkyleneoxy group may preferably be an ethyleneoxy group or a propyleneoxy group.
The polyalkylene oxide group is preferably a polyethylene oxide group, a polypropylene oxide group or a group in which one or more ethylene oxide groups and one or more propylene oxide groups are bonded.
The surfactant having a fluorine atom is preferably a surfactant having a fluoroalkyl group and an alkyleneoxy group, more preferably a surfactant having a perfluoroalkyl group and a polyalkyleneoxy group, and particularly preferably a surfactant having a perfluoroalkyl group and a polyalkyleneoxy group having 4 or more carbon atoms, from the viewpoint of suppressing the occurrence of streaks and the adhesion to the transfer surface at the time of transfer.
The intermediate layer may contain one kind of surfactant alone or two or more kinds of surfactants having fluorine atoms.
The surfactant having a fluorine atom in the intermediate layer preferably contains a compound having a molecular weight of 500 or more, more preferably a compound having a molecular weight of 700 or more, particularly preferably a compound having a molecular weight of 1,000 to 10,000, and from the viewpoint of suppressing the occurrence of streaks and the adhesion between the photosensitive resin layer and the intermediate layer, the surfactant having a fluorine atom preferably contains a compound having a weight average molecular weight (Mw) of 20,000 or less, more preferably a compound having a weight average molecular weight of 10,000 or less, from the viewpoint of the adhesion on the transfer surface at the time of transfer.
From the viewpoint of suppressing the occurrence of streaks and suppressing the precipitation of a surfactant having a fluorine atom, the solubility of the surfactant having a fluorine atom in 100g of water at 25 ℃ is preferably 0.5g or more, and more preferably 1g or more.
As examples of the surfactant having a fluorine atom, Megafac (manufactured by DIC corporation) series can be preferably mentioned.
From the viewpoint of suppressing the occurrence of streaks and the adhesion between the photosensitive resin layer and the intermediate layer, the content of the surfactant having a fluorine atom is preferably 0.05 to 2.0% by mass, more preferably 0.1 to 1.0% by mass, and particularly preferably 0.2 to 0.4% by mass, based on the total mass of the intermediate layer.
[ Water-soluble resin ]
The intermediate layer contains a water-soluble resin.
Examples of the water-soluble resin include cellulose resins, polyvinyl alcohol resins, polyvinyl pyrrolidone resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. Among these, cellulose-based resins are preferable, and at least one resin selected from the group consisting of hydroxypropyl cellulose and hydroxypropyl methyl cellulose is more preferable.
The water-soluble resin is preferably a water-soluble or alkali-soluble acrylic resin. In the present invention, "water-soluble" means that the solubility in 100g of water having a pH of 7.0 at 22 ℃ is 0.1g or more, and "alkali-soluble" means that the solubility of sodium carbonate in 100g of a1 mass% aqueous solution at 22 ℃ is 0.1g or more.
The "water-soluble or alkali-soluble" may be either water-soluble or alkali-soluble, or water-soluble and alkali-soluble.
The solubility of the water-soluble resin in 100g of water having a pH of 7.0 at 22 ℃ is preferably 1g or more, more preferably 5g or more.
From the viewpoint of water solubility or alkali solubility, the water-soluble or alkali-soluble acrylic resin preferably has a hydrophilic group, and more preferably has a structural unit containing a hydrophilic group.
The hydrophilic group is preferably an acid group, a hydroxyl group, a polyalkyleneoxy group, an amide group, a basic group capable of forming a salt, and the like, which can form a salt, and preferably at least an acid group or a hydroxyl group capable of forming a salt from the viewpoint of adhesiveness.
The intermediate layer may contain one kind of the water-soluble resin alone or two or more kinds of the water-soluble resins.
The content of the water-soluble resin is preferably 20 to 100% by mass, and more preferably 50 to 100% by mass, based on the total mass of the intermediate layer, from the viewpoints of the shape of the obtained pattern, the adhesion to the transfer surface at the time of transfer, and the adhesion between the photosensitive resin layer and the intermediate layer.
[ pigment ]
From the viewpoint of ease of confirmation of an exposure pattern, the intermediate layer preferably contains a dye (simply referred to as "dye") having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm in color development and changing the maximum absorption wavelength by an acid, a base, or a radical.
The "dye" changes its maximum absorption wavelength by an acid, a base, or a radical "may mean any of a method in which a dye in a colored state is decolored by an acid, a base, or a radical, a method in which a dye in a decolored state is colored by an acid, a base, or a radical, and a method in which a dye in a colored state is changed to a colored state of another color.
Specifically, the dye may be a compound that develops color by changing from a decolored state by exposure, or may be a compound that develops color by changing from a decolored state by exposure. In this case, the dye may be one in which the state of coloration or decoloration is changed by introducing an acid, a base, or a radical into the intermediate layer by exposure, or may be one in which the state of coloration or decoloration is changed by introducing an acid, a base, or a radical to change the property (for example, pH) in the system. Further, the dye may be one in which an acid, a base, or a radical is directly applied as a stimulus without exposure to light to change the state of color development or discoloration.
Among them, the dye may be a compound that develops color by exposure or a compound that decolors by exposure, but from the viewpoint of visibility, a compound that decolors by exposure is preferable, and a latent dye that decolors by an acid generated from a photoacid generator, that is, a pH-sensitive dye that decolors by a change in pH due to generation of an acid is more preferable.
The pH-sensitive dye can be confirmed by the following method.
0.1g of a dye was dissolved in 100ml of a mixed solution of ethanol and water (ethanol/water: 1/2 (mass ratio)), and 0.1mol/L (1N) of a hydrochloric acid aqueous solution was added thereto to adjust the pH to 1. Titration was carried out with 0.01mol/L (0.01n) aqueous sodium hydroxide solution, and the coloration change and the pH at which the coloration change occurred were confirmed. The pH was measured at 25 ℃ using a pH meter (model: HM-31, manufactured by DKK-TOA CORPORATION).
From the viewpoint of visibility, the dye preferably has a maximum absorption wavelength in the wavelength range of 400nm to 780nm during color development of 550nm or more, more preferably 550nm or more and 700nm or less, and still more preferably 550nm or more and 650nm or less.
The dye may have only one or two or more maximum absorption wavelengths in the wavelength range of 400nm to 780nm in the case of color development. When the dye has two or more maximum absorption wavelengths in the wavelength range of 400nm to 780nm during color development, the maximum absorption wavelength at which the absorbance is the highest among the two or more maximum absorption wavelengths may be 450nm or more.
The method for measuring the maximum absorption wavelength in the present invention is as follows: under atmospheric atmosphere, at 25 ℃, using a spectrophotometer: UV3100 (manufactured by Shimadzu corporation) measures a transmission spectrum in a wavelength range of 400nm to 780nm, and measures a wavelength at which the intensity of light becomes extremely small (maximum absorption wavelength).
Examples of the dye which develops color by exposure to light include colorless compounds.
Examples of the dye decolorized by exposure to light include a leuco compound, a diphenylmethane dye, an oxazine dye, a xanthene dye, an iminotheaquinone dye, an azomethine dye, and an anthraquinone dye.
Among them, a colorless compound is preferable as the coloring matter from the viewpoint of visibility.
Examples of the colorless compound include colorless compounds of triarylmethane (e.g., triphenylmethane), spiropyrane, fluoran, diphenylmethane, rhodamine, indolphthalate, and leucoauramine (leucoauramine). Among them, a colorless compound having a triarylmethane skeleton (triarylmethane-based coloring matter) is preferable, and a triphenylmethane-based coloring matter is more preferable.
The colorless compound is preferably a colorless compound having a lactone ring, a sulftin ring or a sultone ring, in which the lactone ring, the sulftin ring or the sultone ring is opened or closed, and more preferably a colorless compound having a sultone ring, in which the sultone ring is closed and decolorized, from the viewpoint of visibility.
The dye is preferably a water-soluble compound for the purpose of preventing defects due to precipitation of the dye.
The solubility of the dye in 100g of water having a pH of 7.0 at 22 ℃ is preferably 1g or more, more preferably 5g or more.
The intermediate layer may contain one kind of pigment alone or two or more kinds of pigments.
The content of the coloring matter in the intermediate layer is preferably 0.01 to 10% by mass, more preferably 0.1 to 8% by mass, even more preferably 0.5 to 5% by mass, and particularly preferably 1.0 to 3.0% by mass, based on the total mass of the intermediate layer, from the viewpoint of visibility.
[ other surfactants ]
The intermediate layer may contain a surfactant other than the surfactant having a fluorine atom.
As the other surfactant, any of anionic, cationic, nonionic (Nonion) and amphoteric surfactants can be used, and a known surfactant can be used.
From the viewpoint of suppressing the generation of streaks, the content of the other surfactant in the intermediate layer is preferably less than the content of the surfactant having a fluorine atom.
When the other surfactant is contained, the content of the other surfactant is preferably 0.01 mass% or more and less than 2.0 mass% with respect to the total mass of the intermediate layer, from the viewpoint of suppressing the occurrence of streaks and the adhesion to the transfer surface at the time of transfer.
[ inorganic Filler ]
The intermediate layer can comprise an inorganic filler. The inorganic filler in the present invention is not particularly limited. Examples thereof include silica particles, alumina particles, and zirconia particles, and silica particles are more preferable. From the viewpoint of transparency, particles having a small particle diameter are preferable, and particles having an average particle diameter of 100nm or less are more preferable. For example, in the case of a commercially available product, SNOWTEX (registered trademark) is preferably used.
From the viewpoint of the adhesion between the intermediate layer and the photosensitive layer, the volume fraction of the particles in the intermediate layer (the volume fraction of the particles in the intermediate layer) is preferably 5% to 90%, more preferably 10% to 80%, even more preferably 15% to 70%, and particularly preferably 20% to 60% with respect to the total volume of the intermediate layer.
As described later, when the intermediate layer is formed as two layers, the volume fraction of the particles in the entire intermediate layer (the volume fraction of the particles in the intermediate layer) is preferably 2% to 90%, more preferably 3% to 80%, even more preferably 5% to 20%, and particularly preferably 10% to 20% with respect to the total volume of the intermediate layer, from the viewpoint of adhesion between the intermediate layer and the photosensitive layer.
[ pH adjuster ]
The intermediate layer can contain a pH adjuster. By including the pH adjuster, the colored state or the decolored state of the dye in the intermediate layer can be maintained more stably, and the adhesion can be further improved.
The pH adjuster in the present invention is not particularly limited. Examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, organic amines, and organic ammonium salts. From the viewpoint of water solubility, sodium hydroxide is preferred. From the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer, an organic ammonium salt is preferable.
Examples of the organic ammonium salt include a primary ammonium salt, a secondary ammonium salt, a tertiary ammonium salt and a quaternary ammonium salt, and a quaternary ammonium salt is preferable.
The quaternary ammonium salt may, for example, be a tetraalkylammonium hydroxide having a substituent, and specific examples thereof include tetramethylammonium hydroxide, triethylmethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, hexadecyltrimethylammonium hydroxide, choline, benzyltrimethylammonium, benzyltriethylammonium, tris (2-hydroxyethyl) methylammonium hydroxide and the like.
Among them, tetraalkylammonium hydroxide having an alkyl group having 1 to 30 carbon atoms (preferably 10 to 30 carbon atoms, more preferably 10 to 25 carbon atoms) is more preferable. Examples of the substituent having a substituent include an aryl group having 6 to 12 carbon atoms (for example, phenyl group), a hydroxyl group and the like.
[ average thickness of intermediate layer ]
The average thickness of the intermediate layer is preferably 0.3 to 10 μm, more preferably 0.3 to 5 μm, and particularly preferably 0.3 to 2 μm, from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer and pattern formability.
The average thickness of the intermediate layer is preferably smaller than the average thickness of the photosensitive resin layer.
The intermediate layer may have 2 or more layers.
In the case where the intermediate layer has 2 or more layers, the average thickness of each layer is not particularly limited as long as it is within the above range, and of the 2 or more layers in the intermediate layer, the average thickness of the layer closest to the photosensitive resin layer is preferably 0.3 to 10 μm, more preferably 0.3 to 5 μm, and particularly preferably 0.3 to 2 μm, from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation.
In the method of measuring the average thickness of each layer in the present invention, a cross section in a direction perpendicular to the surface direction of the transfer material is observed and measured by a Scanning Electron Microscope (SEM). The average thickness is an average value of 10 or more points of the thickness.
[ method for Forming intermediate layer ]
The intermediate layer in the present invention can be formed by adjusting components necessary for forming the intermediate layer and an intermediate layer-forming composition containing a water-soluble solvent, and applying and drying the intermediate layer. The intermediate layer-forming composition for forming the intermediate layer can be prepared by mixing the respective components and the water-soluble solvent at a predetermined ratio by an arbitrary method and stirring and dissolving the mixture. For example, the composition may be prepared by dissolving each component in a solvent in advance, and then mixing the obtained solutions at a predetermined ratio. The composition prepared as above can also be used after filtration using a filter having a pore size of 3.0 μm or the like.
The intermediate layer can be formed on the temporary support by applying the intermediate layer forming composition to the temporary support and drying the composition. The coating method is not particularly limited, and coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
Intermediate layer forming composition
The intermediate layer-forming composition preferably contains the components contained in the intermediate layer and a water-soluble solvent. The intermediate layer can be formed appropriately by adjusting the viscosity by adding a water-soluble solvent to each component, and by coating and drying.
The water-soluble solvent may, for example, be water or an alcohol compound having 1 to 6 carbon atoms, and preferably contains water. The alcohol compound having 1 to 6 carbon atoms may, for example, be methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol or n-hexanol, and is preferably at least one compound selected from the group consisting of methanol, ethanol, n-propanol and isopropanol.
< photosensitive resin layer >
The transfer material according to the present invention has a photosensitive resin layer.
The photosensitive resin layer in the present invention is a positive photosensitive resin layer, and a known positive photosensitive resin layer can be used. From the viewpoint of sensitivity and resolution, the photosensitive resin layer used in the present invention preferably contains an acid-decomposable resin, that is, a polymer having a structural unit containing an acid group protected by an acid-decomposable group and a photoacid generator, and more preferably a chemically amplified positive photosensitive resin layer containing a polymer having a structural unit containing an acid group protected by an acid-decomposable group and a photoacid generator.
With respect to the photoacid generators such as onium salts and oxime sulfonate compounds described later, since an acid generated by the induction of active radiation (active light) acts as a catalyst for the deprotection of a protected acid group in the polymer, the acid generated by the action of one photon contributes to a plurality of deprotection reactions, and the quantum yield exceeds 1, for example, has a large value such as a square of 10, and as a result of so-called chemical amplification, high sensitivity can be obtained.
On the other hand, when a quinone diazide compound is used as a photoacid generator for inducing activation light, a carboxyl group is generated by successive type photochemical reaction, but the quantum yield thereof is required to be 1 or less, and the compound does not belong to a chemically amplified type.
[ Polymer A1 having a structural Unit containing an acid group protected with an acid-decomposable group ]
The positive photosensitive resin layer preferably contains a polymer (also simply referred to as "polymer a 1") having a structural unit (also referred to as "structural unit a") containing an acid group protected by an acid-decomposable group.
The positive photosensitive resin layer may contain another polymer in addition to the polymer a1 having the structural unit a. In the present invention, the polymer a1 having the structural unit a and other polymers are also collectively referred to as "polymer components".
With respect to the polymer a1, an acid group protected by an acid-decomposable group in the polymer a1 is subjected to deprotection reaction and is reflected as an acid group by the action of an acidic substance such as a catalyst amount of acid generated by exposure. The acid group can be dissolved in the developer.
The polymer a1 is preferably an addition polymerization type resin, and more preferably a polymer having a structural unit derived from (meth) acrylic acid or an ester thereof. In addition, the resin composition may have a structural unit other than a structural unit derived from (meth) acrylic acid or an ester thereof, for example, a structural unit derived from a styrene compound, a structural unit derived from a vinyl compound, or the like.
Preferred embodiments of the structural unit a are described below.
Structural unit A-
The polymer component preferably contains a polymer a1 having a structural unit a containing an acid group protected by an acid-decomposable group. By including the polymer a1 having the structural unit a in the photosensitive resin layer, a chemically amplified positive photosensitive resin layer with extremely high sensitivity can be obtained.
The polymer a1 contained in the positive photosensitive resin layer may be only one type, or two or more types.
The acid group and the acid-decomposable group in the present invention are not particularly limited, and known acid groups and acid-decomposable groups can be used. Specific examples of the acid group include a carboxyl group and a Phenolic hydroxyl group (also referred to as "Phenolic hydroxyl group"). Further, as the acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an acetal-type functional group such as a 1-alkoxyalkyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group) or a group which is relatively hardly decomposed by an acid (for example, a tert-alkyl group such as a tert-butyl group, or a tert-alkoxycarbonyl group such as a tert-butoxycarbonyl group) can be used
Among these, the acid-decomposable group is preferably a group having a structure protected in the form of an acetal group.
Further, the acid-decomposable group is preferably an acid-decomposable group having a molecular weight of 300 or less, from the viewpoint of suppressing variation in line width of the conductive wiring when applied to the formation of a conductive pattern.
From the viewpoint of sensitivity and resolution, the structural unit a having an acid group protected with an acid-decomposable group is preferably a structural unit represented by any one of the following formulae a1 to A3.
[ chemical formula 2]
Figure BDA0003069266620000151
In the formula A1, R11And R12Each independently represents a hydrogen atom, an alkyl group or an aryl group, R11And R12At least one of which is alkyl or aryl, R13Represents alkyl or aryl, R11Or R12And R13May be linked to form a cyclic ether, R14Represents a hydrogen atom or a methyl group, X1Represents a single bond or a divalent linking group, R15Represents a substituent, and n represents an integer of 0 to 4.
In the formula A2, R21And R22Each independently represents a hydrogen atom, an alkyl group or an aryl group, R21And R22At least one of which is alkyl or aryl, R23Represents alkyl orAryl radical, R21Or R22And R23May be linked to form a cyclic ether, R24Each independently represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.
In the formula A3, R31And R32Each independently represents a hydrogen atom, an alkyl group or an aryl group, R31And R32At least one of which is alkyl or aryl, R33Represents alkyl or aryl, R31Or R32And R33May be linked to form a cyclic ether, R34Represents a hydrogen atom or a methyl group, X0Represents a single bond or a divalent linking group.
From the viewpoint of the acid decomposition rate and sensitivity, the acid group protected by the acid-decomposable group is preferably a structure protected in an acetal form, that is, a carboxyl group protected by the acid-decomposable group.
In the formula A3, in R31Or R32In the case of an alkyl group, the number of carbon atoms is preferably 1 to 10. At R31Or R32In the case of aryl, phenyl is preferred. R31And R32Each of which is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In the formula A3, R33Represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
And, R31~R33The alkyl group and the aryl group in (1) may have a substituent.
In the formula A3, R31Or R32And R33May be linked to form a cyclic ether, preferably R31Or R32And R33Linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In the formula A3, X0Represents a single bond or an arylene group, preferably a single bond. The arylene group may have a substituent.
The structural unit a represented by the above formula a3 is a structural unit having a carboxyl group protected by an acid-decomposable group. By the polymer a1 containing the structural unit a represented by formula A3, the sensitivity at the time of pattern formation is excellent, and the resolution is more excellent.
In the formula A3, R34Represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the glass transition temperature (Tg) of the polymer a1 can be further lowered.
More specifically, R in the formula A3 is relative to the total amount of the structural units A contained in the polymer A134The structural unit that is a hydrogen atom is preferably 20 mass% or more.
R in the structural unit A and in the formula A334The content (content ratio: mass ratio) of the structural unit which is a hydrogen atom can be determined by13C-nuclear magnetic resonance spectroscopy (NMR) measurement was carried out to confirm the intensity ratio of the peak intensities calculated by a conventional method.
Preferable embodiments of the formulas a1 to A3 include paragraphs 0044 to 0058 of international publication No. 2018/179640.
In the formulae a1 to A3, the acid-decomposable group is preferably a group having a cyclic structure, more preferably a group having a tetrahydrofuran ring or a tetrahydropyran ring structure, still more preferably a group having a tetrahydrofuran ring structure, and particularly preferably a tetrahydrofuranyl group, from the viewpoint of sensitivity.
The content of the structural unit a in the polymer component containing the polymer a1 is preferably 10 to 90% by mass, more preferably 10 to 70% by mass, still more preferably 15 to 50% by mass, and particularly preferably 20 to 40% by mass, based on the total mass of the polymer component. Within the above range, the resolution is further improved.
The content (content ratio: mass ratio) of the structural unit A in the polymer component comprising the polymer A1 can be determined by13C-NMR measurement was confirmed by using the intensity ratio of peak intensities calculated by a conventional method.
Structural unit B-
Polymer a1 may contain structural units having acid groups (also referred to as "structural unit B").
The structural unit B is a structural unit containing an acid group which is not protected by a protecting group such as an acid-decomposable group, that is, an acid group having no protecting group. Since the polymer a1 contains the structural unit B, the sensitivity at the time of pattern formation is improved, and the polymer a1 is easily dissolved in an alkaline developer in a developing step after pattern exposure, thereby shortening the developing time.
The acid group in the present specification means a proton-dissociative group having a pKa of 12 or less. It is preferable that the acid group is incorporated into the polymer a1 using a monomer capable of forming an acid group as a structural unit (structural unit B) containing an acid group.
From the viewpoint of improving the sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. Also, the pKa of the acid group is preferably-5 or more.
The polymer a1 contains the structural unit a and the structural unit B having an acid group not containing a protective group as copolymerization components, and by setting the glass transition temperature to 90 ℃ or lower, the positive photosensitive resin layer containing the polymer a1 maintains good transferability and releasability from a temporary support, and further improves resolution and sensitivity in pattern formation.
Examples of the acid group include a carboxyl group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a sulfonimide group. Among them, at least one acid group selected from the group consisting of a carboxyl group and a phenolic hydroxyl group is preferable.
The introduction of the structural unit having an acid group into the polymer a1 can be performed by copolymerizing a monomer having an acid group.
The structural unit containing an acid group as the structural unit B is more preferably a structural unit in which an acid group is substituted with respect to a structural unit derived from a styrene compound or a structural unit derived from a vinyl compound, or a structural unit derived from (meth) acrylic acid.
The structural unit B is preferably a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group, from the viewpoint of further improving the sensitivity in pattern formation.
The monomer having an acid group capable of forming the structural unit B is not limited to the examples described above.
The structural unit B contained in the polymer a1 may be one type, or two or more types.
The polymer a1 preferably contains the structural unit having an acid group (structural unit B) in an amount of 0.01 to 20% by mass, more preferably 0.01 to 15% by mass, and still more preferably 0.01 to 10% by mass, based on the total mass of the polymer a 1. Within the above range, the pattern formability is favorably changed.
The content (content ratio: mass ratio) of the structural unit B in the polymer A1 can be determined by13C-NMR measurement was confirmed by using the intensity ratio of peak intensities calculated by a conventional method.
Other structural units-
The polymer a1 may contain other structural units (hereinafter, may be referred to as a structural unit C) than the structural unit a and the structural unit B described above, within a range not impairing the effects of the transfer material according to the present invention.
The monomer forming the structural unit C is not particularly limited, and examples thereof include styrenes, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, aryl (meth) acrylates, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic anhydrides, groups having an aliphatic cyclic skeleton, and other unsaturated compounds.
By using the structural unit C, the properties of the polymer a1 can be adjusted by adjusting at least one of the type and the content. In particular, the Tg of the polymer a1 can be easily adjusted by appropriately using the structural unit C.
By setting the glass transition temperature to 120 ℃ or lower, the photosensitive resin layer containing the polymer a1 maintains good transferability and removability from the temporary support, and also makes good changes in resolution and sensitivity during pattern formation.
The polymer a1 may contain only one kind of the structural unit C, or may contain two or more kinds of the structural unit C.
With respect to the structural unit C, specifically, examples of the structural units include structural units formed by polymerizing styrene, methylstyrene, α -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl benzoate vinyl ester, ethyl benzoate vinyl ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, and ethylene glycol monoacetoacetate mono (meth) acrylate. Examples of the compounds include those described in paragraphs 0021 to 0024 of Japanese patent application laid-open No. 2004-264623.
The structural unit C preferably contains a structural unit having a basic group from the viewpoint of resolution.
The basic group is preferably a group having a nitrogen atom, more preferably an aliphatic amino group, an aromatic amino group or a nitrogen-containing heteroaromatic ring group, still more preferably an aliphatic amino group or a nitrogen-containing heteroaromatic ring group, and particularly preferably an aliphatic amino group, from the viewpoint of resolution.
The aliphatic amino group may be any of a primary amino group, a secondary amino group, or a tertiary amino group, and is preferably a secondary amino group or a tertiary amino group from the viewpoint of resolution.
The aromatic amino group is preferably an anilino group, a monoalkylphenylamino group or a dialkylanilino group, and more preferably a monoalkylphenylamino group or a dialkylanilino group.
The nitrogen-containing heteroaromatic ring in the nitrogen-containing heteroaromatic ring group is preferably a pyridine ring, an imidazole ring or a triazole ring, more preferably a pyridine ring or an imidazole ring, and particularly preferably a pyridine ring.
The nitrogen-containing heteroaromatic ring group may have a substituent on the nitrogen-containing heteroaromatic ring. The substituent is not particularly limited, but is preferably an alkyl group, and more preferably a methyl group.
Specific examples of the monomer forming a structural unit having a basic group include 1, 2, 2, 6, 6-pentamethyl-4-piperidyl methacrylate, 2- (dimethylamino) ethyl methacrylate, 2, 2, 6, 6-tetramethyl-4-piperidyl acrylate, 2, 2, 6, 6-tetramethyl-4-piperidyl methacrylate, 2, 2, 6, 6-tetramethyl-4-piperidyl acrylate, 2- (diethylamino) ethyl methacrylate, 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate, N-piperidyl methacrylate, and the like, N- (3-diethylamino) propyl methacrylate, N- (3-diethylamino) propyl acrylate, 2- (diisopropylamino) ethyl methacrylate, 2-morpholinoethyl acrylate, N- [3- (dimethylamino) propyl ] acrylamide, allylamine, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole, 1-ethylene-1, 2, 4-triazole and the like.
In addition, as the structural unit C, a structural unit having an aromatic ring or a structural unit having an aliphatic ring skeleton is preferable from the viewpoint of improving the electrical characteristics of the obtained transfer material. Specific examples of the monomer forming these structural units include styrene, methylstyrene, α -methylstyrene, dicyclopentyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate. Among these, as the structural unit C, a structural unit derived from cyclohexyl (meth) acrylate is preferably exemplified.
In addition, as a monomer forming the structural unit C, for example, alkyl (meth) acrylate is preferable from the viewpoint of adhesiveness. Among these, alkyl (meth) acrylates having an alkyl group having 4 to 12 carbon atoms are more preferable from the viewpoint of adhesion. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate may be mentioned.
The content of the structural unit C in the polymer component is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 50% by mass or less, based on the total mass of the polymer component. The lower limit may be 0 mass%, but is preferably 10 mass%, and more preferably 20 mass% or more. Within the above range, the resolution and the adhesion are further improved.
Preferred examples of the polymer a1 in the present invention will be described below, but the present invention is not limited to the examples below. In order to obtain preferable physical properties, the ratio of the structural units in the following exemplary compounds and the weight average molecular weight can be appropriately selected.
[ chemical formula 3]
Figure BDA0003069266620000201
Glass transition temperature of polymer a 1: tg-
From the viewpoint of further exhibiting the resolution and the effects of the present invention, the glass transition temperature (Tg) of the polymer a1 in the present invention is preferably 20 ℃ or higher, more preferably 20 ℃ or higher and 90 ℃ or lower, still more preferably 20 ℃ or higher and 60 ℃ or lower, and particularly preferably 30 ℃ or higher and 50 ℃ or lower.
As a method for adjusting Tg of the polymer in the present invention to the above-described preferable range, for example, Tg of the target polymer can be controlled by FOX formula in accordance with the mass ratio of Tg of the homopolymer of each structural unit of the target polymer to each structural unit.
With respect to the formula FOX,
when Tg of the homopolymer of the first structural unit contained in the polymer is Tg1, mass% of the copolymer of the first structural unit is W1, Tg of the homopolymer of the second structural unit is Tg2, and mass% of the copolymer of the second structural unit is W2, Tg0(K) of the copolymer containing the first structural unit and the second structural unit can be estimated from the following equation.
FOX formula: 1/Tg0 ═ W1/Tg1) + (W2/Tg2)
By adjusting the kind and mass percentage of each structural unit contained in the copolymer using the formula FOX already described, a copolymer having a desired Tg can be obtained.
Further, the Tg of the polymer can be adjusted by adjusting the weight average molecular weight of the polymer.
Acid number of Polymer A1-
From the viewpoint of resolution, the acid value of the polymer a1 is preferably 0mgKOH/g or more and 100mgKOH/g or less, more preferably 0mgKOH/g or more and 50mgKOH/g or less, still more preferably 0mgKOH/g or more and 20mgKOH/g or less, and particularly preferably 0mgKOH/g or more and 10mgKOH/g or less.
The acid value of the polymer in the present invention represents the mass of potassium hydroxide required for neutralizing 1g of the acidic component of the polymer. Specifically, a measurement sample was dissolved in a tetrahydrofuran/water 9/1 (volume ratio) mixed solvent, and the obtained solution was subjected to neutralization titration with a 0.1mol/L aqueous solution of sodium hydroxide AT 25 ℃ using a potentiometric titration apparatus (trade name: AT-510, KYOTO electroinc. The inflection point of the titration pH curve was used as the titration end point, and the acid value was calculated by the following formula.
A=56.11×Vs×0.1×f/w
A: acid value (mgKOH/g)
Vs: amount of 0.1mol/L aqueous sodium hydroxide solution (mL) required for titration
f: titer of 0.1mol/L aqueous sodium hydroxide solution
w: the mass (g) of the sample was measured (conversion of solid content)
Molecular weight of polymer a 1: mw-
From the viewpoint of further exhibiting the effects of the present invention, the molecular weight of the polymer a1 is preferably 10,000 or more and 60,000 or less, more preferably 15,000 or more and 60,000 or less, and further preferably 20,000 or more and 50,000 or less, in terms of weight average molecular weight in terms of polystyrene.
The weight average molecular weight of the polymer in the present invention can be measured by GPC (gel permeation chromatography), and various commercially available apparatuses can be used as the measuring apparatus, and the contents of the apparatuses and the measuring techniques are well known to those skilled in the art.
For the measurement of the weight average molecular weight by Gel Permeation Chromatography (GPC), HLC (registered trademark) -8220GPC (TOSOH CORPORATION 0N) can be used as a measuring device, and a column in which one TSKgel (registered trademark) Super HZM-M (4.6mmID × 15cm, TOSOH CORPORATION), Super HZ4000(44.6mmID × 15cm, TOSOH CORPORATION), Super HZ3000(4.6mmID × 15cm, TOSOH CORPORATION), and toser HZ2000(4.6mmID × 15cm, TOSOH CORPORATION) are connected in series can be used as a column, and THF (tetrahydrofuran) can be used as an eluent.
The measurement conditions were 0.2 mass% for the sample concentration, 0.35ml/min for the flow rate, 10. mu.L for the sample injection amount, and 40 ℃ for the measurement temperature, and a differential Refractive Index (RI) detector was used.
The calibration curve can be obtained using "standard TSK standard, polystyrene" manufactured by TOSOH CORPORATION: any of 7 samples of "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500" and "A-1000" was prepared.
The ratio (dispersity) of the number average molecular weight to the weight average molecular weight of the polymer A1 is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.
Process for the preparation of Polymer A1
The method for producing the polymer a1 (synthesis method) is not particularly limited, and can be synthesized by polymerizing a monomer for forming the structural unit a and, if necessary, a polymerizable monomer for forming another structural unit C in an organic solvent using a polymerization initiator, as an example. Further, the synthesis can be performed by a so-called polymer reaction.
From the viewpoint of suppressing the occurrence of streaks and the adhesion on the transfer surface at the time of transfer, the content of the polymer component in the positive photosensitive resin layer in the present invention is preferably 75% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 90% by mass to 99.9% by mass, based on the total mass of the photosensitive resin layer.
From the viewpoint of suppressing wiring defects and resolution, the content of the polymer a1 in the positive photosensitive resin layer is preferably 75 to 99.9 mass%, more preferably 80 to 99 mass%, and particularly preferably 90 to 95 mass%, with respect to the total mass of the positive photosensitive resin layer.
[ other polymers ]
The positive photosensitive resin layer may contain, as a polymer component, a polymer (sometimes referred to as "other polymer") that does not include a structural unit having an acid group protected by an acid-decomposable group, in addition to the polymer a1, within a range that does not impair the effects of the transfer material according to the present invention.
Unless otherwise specified, the polymer component in the present invention means that other polymers added as needed are included in addition to the polymer a 1. Further, compounds corresponding to a crosslinking agent, a dispersant and a surfactant described later are not included in the polymer component even if they are polymer compounds.
When the positive photosensitive resin layer contains another polymer, the content of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less, of the total polymer components.
The positive photosensitive resin layer may contain one kind of polymer, or two or more kinds of other polymers in addition to the polymer a 1.
As the other polymer, for example, polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P and SMA 3840F (described above, manufactured by Sartomer company, Inc.), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920 and ARON UC-3080 (described above, manufactured by TOAGOSEI CO., LTD.), JonCryil 690, JonCryil 678, JonCryil 67 and JonCryil 586 (described above, manufactured by BASF corporation), and the like can be used.
[ photoacid generators ]
The positive photosensitive resin layer preferably contains a photoacid generator.
The photoacid generator used in the present invention is a compound that can generate an acid by irradiation with an active ray such as ultraviolet light, far ultraviolet light, X-ray, or electron beam.
The photoacid generator used in the present invention is preferably a compound that generates an acid by sensing an activating light beam having a wavelength of 300nm or more, preferably 300nm to 450nm, but the chemical structure thereof is not limited. The photoacid generator which does not directly sense the activation light having a wavelength of 300nm or more can be preferably used in combination with a sensitizer as long as it is a compound which senses the activation light having a wavelength of 300nm or more by using the sensitizer in combination and generates an acid.
The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and particularly preferably a photoacid generator that generates an acid having a pKa of 2 or less. The lower limit of the pKa is not particularly limited, but is preferably at least-10.0, for example.
Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.
Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Among these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.
As the ionic photoacid generator, the ionic photoacid generators described in paragraphs 0114 to 0133 of Japanese patent application laid-open No. 2014-085643 can also be preferably used.
Examples of the nonionic photoacid generator include trichloromethyl s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, the photoacid generator is preferably an oxime sulfonate compound from the viewpoint of sensitivity, resolution, and adhesion. Specific examples of the trichloromethyl s-triazine, diazomethane compound and imide sulfonate compound include compounds described in paragraphs 0083 to 0088 of Japanese patent laid-open publication No. 2011-221494.
As the oxime sulfonate compound, the compounds described in paragraphs 0084 to 0088 of International publication No. 2018/179640 can be preferably used.
The photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and more preferably contains an oxime sulfonate compound, from the viewpoint of sensitivity and resolution.
Further, as a preferable photoacid generator, for example, a photoacid generator having the following structure can be exemplified.
[ chemical formula 4]
Figure BDA0003069266620000251
The positive photosensitive resin layer may contain one kind of the photoacid generator alone, or may contain two or more kinds of the photoacid generator.
From the viewpoint of sensitivity and resolution, the content of the photoacid generator in the positive photosensitive resin layer is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, with respect to the total mass of the positive photosensitive resin layer.
[ other additives ]
The positive photosensitive resin layer in the present invention may contain other additives as necessary, in addition to the polymer component containing the polymer a1, the photoacid generator, and the solvent.
As the other additives, known additives can be used, and examples thereof include plasticizers, sensitizers, heterocyclic compounds, alkoxysilane compounds, basic compounds, rust inhibitors, and surfactants.
Examples of the plasticizer, sensitizer, heterocyclic compound and alkoxysilane compound include those described in paragraphs 0097 to 0119 of International publication No. 2018/179640.
Basic compounds-
The positive photosensitive resin layer preferably further contains an alkaline compound.
The basic compound can be used by being arbitrarily selected from among basic compounds used for chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Examples of these compounds include those described in paragraphs 0204 to 0207 of Japanese patent application laid-open publication No. 2011-221494, and these contents are incorporated in the present specification.
Specifically, examples of the aliphatic amine include di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, dicyclohexylamine, dicyclohexylmethylamine and the like.
Examples of the aromatic amine include aniline, benzylamine, N-dimethylaniline and diphenylamine.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2, 4, 5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxoquinoline, pyrazine, pyrazole, pyridazine, pudding, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1, 5-diazabicyclo [4.3.0] -5-nonene and 1, 8-diazabicyclo [5.3.0] -7-undecene.
Further, as the basic compound, N-cyclohexyl-N' - [2- (4-morpholinyl) ethyl ] thiourea (CMTU) can be preferably used. Further, a commercial product of CMTU may be, for example, a product manufactured by New chemical tracing co., ltd.
As the basic compound, a benzotriazole compound is preferable from the viewpoint of being suitable for the linearity of the conductive wiring at the time of forming the conductive pattern.
The benzotriazole compound is not particularly limited as long as it has a benzotriazole skeleton, and a known benzotriazole compound can be used.
Examples of the benzotriazole compound include 1, 2, 3-benzotriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] benzotriazole, 5-carboxybenzotriazole, 1- (hydroxymethyl) -1H-benzotriazole, 1-acetyl-1H-benzotriazole, 1-aminobenzotriazole, 9- (1H-benzotriazol-1-ylmethyl) -9H-carbazole, 1-chloro-1H-benzotriazole, 1- (2-pyridyl) benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-ethylbenzotriazole, 1- (1' -hydroxyethyl) benzotriazole, 1- (2-pyridyl) benzotriazole, and mixtures thereof, 1-propylbenzotriazole, 1- (1 ' -hydroxypropyl) benzotriazole, 1- (2 ' -hydroxypropyl) benzotriazole, 1- (3 ' -hydroxypropyl) benzotriazole, 4-hydroxy-1H-benzotriazole, 5-methyl-1H-benzotriazole, methylbenzotriazole-5-carboxylate, ethylbenzotriazole-5-carboxylate, t-butylbenzotriazole-5-carboxylate, cyclopentylethyl-benzotriazole-5-carboxylate, 1H-benzotriazole-4-sulfonic acid, 1H-benzotriazole-1-acetonitrile, 1H-benzotriazole-1-carboxaldehyde, 2-methyl-2H-benzotriazole, methyl-1-carboxylate, methyl-2H-benzotriazole, methyl-1-methyl-1, 2-ethyl-2H-benzotriazole, and the like.
The positive photosensitive resin layer may contain one kind of the basic compound alone or two or more kinds of the basic compounds.
The content of the basic compound is preferably 0.001 to 5% by mass, and more preferably 0.005 to 3% by mass, based on the total mass of the positive photosensitive resin layer.
Surfactants-
From the viewpoint of thickness uniformity, the positive photosensitive resin layer preferably contains a surfactant.
As the surfactant, any of anionic, cationic, nonionic (Nonion) or amphoteric may be used, and a preferable surfactant is a nonionic surfactant.
Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. Further, the following products are commercially available under the trade names KP (Shin-Etsu CHEMICAl co., Ltd.), Polyflow (KYOEISHA CHEMICAL CO., LTD., manufactured by Kyop (Jemco Inc.), Megafac (DIC corporation), F1uorad (manufactured by Sumitomo 3M Limited), Asahiguard, Surflow (ASAHI GLASS CO., manufactured by LTD., manufactured by Kyox (OMNOVA Solutions Inc.), SH-8400(Dow burning Toray co., manufactured by Ltd.), and the like.
Examples of the surfactant include surfactants described in paragraphs 0120 to 0125 of International publication No. 2018/179640.
As a commercially available surfactant, MegafacF-552 or F-554 (see DIC corporation) can be used, for example.
The surfactant described in paragraph 0017 of japanese patent No. 4502784 and paragraphs 0060 to 0071 of japanese patent application laid-open No. 2009-237362 may also be used.
The positive photosensitive resin layer may contain one kind of surfactant alone or two or more kinds of surfactants.
The content of the surfactant is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and still more preferably 0.01% by mass to 3% by mass, based on the total mass of the positive photosensitive resin layer.
In addition, as other additives, known additives such as metal oxide particles, an anti-cyanating agent, a dispersant, an acid extender, a development accelerator, conductive fibers, a colorant, a thermal radical polymerization initiator, a thermal acid generator, an ultraviolet absorber, a thickener, a crosslinking agent, and an organic or inorganic anti-settling agent can be added to the positive photosensitive resin layer in the present invention.
Preferred embodiments of these components are described in paragraphs 0165 to 0184 of Japanese patent application laid-open No. 2014-085643, the contents of which are incorporated herein by reference.
Further, the positive photosensitive resin layer in the transfer material according to the present invention may contain a solvent. In the case where a positive photosensitive resin layer is formed from a photosensitive resin composition containing a solvent, the solvent may remain.
The content of the solvent in the positive photosensitive resin layer is preferably 5% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less, based on the total mass of the photosensitive resin layer.
< average thickness of Positive photosensitive resin layer >)
The average thickness of the positive photosensitive resin layer is preferably 0.5 to 20 μm. When the average thickness of the positive photosensitive resin layer is 20 μm or less, the pattern resolution is more excellent, and when it is 0.5 μm or more, it is preferable from the viewpoint of pattern linearity.
The average thickness of the positive photosensitive resin layer is more preferably 0.8 to 15 μm, and particularly preferably 1.0 to 10 μm.
< method for Forming Positive photosensitive resin layer >)
The positive photosensitive resin layer in the present invention can be formed by adjusting a photosensitive resin composition containing a component and a solvent necessary for forming the positive photosensitive resin layer, and applying and drying the composition. Specifically, the photosensitive resin composition for forming a positive photosensitive resin layer can be prepared by mixing and stirring and dissolving the respective components and the solvent at an arbitrary ratio and by an arbitrary method. For example, the components may be prepared as solutions in which the components are dissolved in a solvent in advance, and the obtained solutions may be mixed at a predetermined ratio to prepare a composition. The composition prepared as described above may be filtered using, for example, a filter having a pore size of 0.2 to 30 μm.
The positive photosensitive resin layer in the present invention can be formed by applying the photosensitive resin composition to a temporary support or a cover film and drying the applied composition.
The coating method is not particularly limited, and coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
Further, another layer described later may be formed on the temporary support or the cover film, and the photosensitive resin layer may be formed.
[ photosensitive resin composition ]
The photosensitive resin composition preferably contains components and a solvent contained in the positive photosensitive resin layer. The photosensitive resin layer can be appropriately formed by adjusting the viscosity by adding a solvent to each component, coating, and drying.
-solvent-
Examples of the solvent include known solvents such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl-n-butyl ether, propylene glycol methyl-n-propyl ether, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether acetate, 3-methoxybutyl ether acetate, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol diacetate, diethylene glycol monoethyl ether acetate, dipropylene glycol dimethyl ether, and 1, 3-butanediol diacetate, and the solvents described in paragraphs 0092 to 0094 of International publication No. 2018/179640.
The solvent preferably contains a solvent or a mixture thereof having a vapor pressure of 1kPa to 16kPa at 20 ℃. The solvent having a vapor pressure at 20 ℃ of 1 to 16kPa preferably includes ethyl acetate, propyl acetate, isopropyl acetate, isobutyl acetate, butyl acetate, tert-butyl acetate, cyclopentyl methyl ether, diisopropyl ether, propylene glycol monoethyl ether, methyl n-butyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, toluene, Propylene Glycol Monomethyl Ether Acetate (PGMEA), Propylene Glycol Monomethyl Ether (PGME), cyclohexanone, 1, 2-propylene glycol diacetate, 1, 3-butylene glycol diacetate, 1, 6-hexanediol diacetate, triacetin, dipropylene glycol n-butyl ether, diethylene glycol monobutyl ether acetate, and the like.
One solvent that can be used in the present invention may be used alone or two solvents may be used in combination.
The content of the solvent in coating the photosensitive resin composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition.
< temporary support >
The transfer material according to the present invention includes a temporary support.
The temporary support is a support that supports the intermediate layer and the photosensitive resin layer and can be peeled off.
The temporary support used in the present invention preferably has light-transmitting properties from the viewpoint that when the intermediate layer and the photosensitive resin layer are pattern-exposed, the intermediate layer and the photosensitive resin layer can be exposed through the temporary support.
Having light transmittance means that the transmittance of the dominant wavelength of light used in pattern exposure is 50% or more, and from the viewpoint of improving exposure sensitivity, the transmittance of the dominant wavelength of light used in pattern exposure is preferably 60% or more, and more preferably 70% or more. The transmittance may be measured by using OTSUKA ELECTRONICS co, LTD MCPD Series.
The temporary support may, for example, be a glass substrate, a resin film, or paper, and the resin film is particularly preferred from the viewpoint of strength, flexibility, and the like. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, the biaxially stretched polyethylene terephthalate film is particularly preferable.
The average thickness of the temporary support is not particularly limited, but is preferably in the range of 5 μm to 200 μm, and more preferably in the range of 10 μm to 150 μm in view of easy handling, versatility and the like.
The thickness of the temporary support may be selected depending on the material, from the viewpoints of the strength of the support, the flexibility required for bonding to the circuit wiring forming substrate, the light transmittance required in the first exposure step, and the like.
A preferred embodiment of the temporary support is described in, for example, paragraphs 0017 to 0018 of japanese patent application laid-open No. 2014-085643, the contents of which are incorporated in the present invention.
< cover film >
The transfer material according to the present invention preferably has a cover film on a surface of the transfer material opposite to the surface on which the temporary support is provided.
The cover film may, for example, be a resin film or paper, and a resin film is particularly preferable from the viewpoint of strength and flexibility. Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, polyethylene film, polypropylene film and polyethylene terephthalate film are preferable.
The average thickness of the coating film is not particularly limited, and is preferably 1 μm to 2mm, for example.
< other layer >
The transfer material according to the present invention may have a layer other than the above (hereinafter, also referred to as "other layer"). As the other layer, a contrast enhancement layer, a thermoplastic resin layer, or the like can be exemplified.
A preferable mode of the contrast enhancement layer is described in paragraph 0134 of international publication No. 2018/179640; preferable embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of Japanese patent laid-open No. 2014-085643; and, regarding the preferred mode of the other layers, it is described in paragraphs 0194 to 0196 of japanese patent application laid-open No. 2014-085643, the contents of which are incorporated in the present specification.
Here, referring to fig. 1, an example of the layer structure of the transfer material according to the present invention is schematically shown.
The transfer material 100 shown in fig. 1 is formed by laminating a temporary support 10, an intermediate layer 12, a photosensitive resin layer 14, and a cover film 16 in this order.
(method for manufacturing resin pattern and method for manufacturing circuit wiring)
The method for producing a resin pattern according to the present invention is not particularly limited as long as it is a method for producing a resin pattern using the transfer material according to the present invention, and the method preferably includes, in order: a step of bringing an outermost layer on the side having the photosensitive resin layer with respect to the temporary support in the transfer material according to the present invention into contact with a substrate and bonding the outermost layer to the substrate (hereinafter, sometimes referred to as "bonding step"); a step of pattern-exposing the photosensitive resin layer (hereinafter, may be referred to as an "exposure step"); and a step of forming a pattern by developing the exposed photosensitive resin layer (hereinafter, may be referred to as a "developing step").
In the method for manufacturing a resin pattern according to the present invention, the substrate is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on a surface thereof.
The method for manufacturing a circuit wiring according to the present invention is not particularly limited as long as it is a method for manufacturing a circuit wiring using the transfer material according to the present invention, and the method preferably includes, in order: a step of bringing an outermost layer on the side having the photosensitive resin layer with respect to the temporary support in the transfer material according to the present invention into contact with a substrate having a conductive layer and bonding the outermost layer to the substrate; a step of pattern-exposing the photosensitive resin layer; developing the exposed photosensitive resin layer to form a pattern; and a step of etching the conductive layer in a region where the pattern is not arranged (hereinafter, may be referred to as an "etching step").
In the method for manufacturing a circuit wiring according to the present invention, the substrate is preferably a substrate having the conductive layer on a surface thereof.
The method for manufacturing a resin pattern according to the present invention and the method for manufacturing a circuit wiring according to the present invention preferably include a step of peeling off the temporary support after the step of bonding the resin pattern to the substrate and before the step of forming the pattern.
The photosensitive resin layer is a positive type in which a portion not irradiated with the activation light remains as an image. In the positive photosensitive resin layer, since the solubility of the exposed portion is improved by using a photosensitive agent or the like which generates an acid by irradiation with an activating light, for example, an activating light, neither the exposed portion nor the unexposed portion is cured at the time of pattern exposure, and when the obtained pattern shape is defective, the substrate can be reused (reworked) by full-surface exposure or the like. Further, the technique of forming a different pattern by re-exposing the remaining photosensitive resin layer cannot be realized unless it is a positive photosensitive resin layer, and therefore, in the method for producing a resin pattern according to the present invention or the method for producing a circuit wiring according to the present invention, a method of performing exposure twice or more is preferable.
As a mode of performing exposure twice or more, the following modes can be exemplified.
The method of manufacturing a circuit wiring according to the present invention preferably includes repeating the 4 steps of the bonding step, the exposure step, the development step, and the etching step a plurality of times as 1 set.
In the method for manufacturing a circuit wiring according to the present invention, it is preferable to perform 4 steps of the bonding step, the exposure step, the development step, and the etching step, and then further perform the exposure step, the development step, and the etching step on the pattern.
< bonding step >
The method for producing a resin pattern according to the present invention or the method for producing a circuit wiring according to the present invention preferably includes a step (bonding step) of bringing an outermost layer on the side having the photosensitive resin layer with respect to the temporary support in the transfer material according to the present invention into contact with a substrate, preferably a substrate having a conductive layer, and bonding the outermost layer to the substrate.
In the bonding step, the conductive layer is preferably pressure-bonded so as to be in contact with the outermost layer of the transfer material according to the present invention on the side having the photosensitive resin layer with respect to the temporary support. In the above aspect, the photosensitive resin layer with a pattern formed after exposure and development can be preferably used as an etching resist in etching the conductive layer.
The method for pressure-bonding the substrate and the transfer material is not particularly limited, and a known transfer method and lamination method can be used.
Specifically, for example, the outermost layer of the transfer material on the side having the photosensitive resin layer with respect to the temporary support is superimposed on the substrate, and the pressing or pressing and heating by a roller or the like are performed. For the bonding, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator capable of further improving productivity can be used.
The pressure and temperature in the bonding step are not particularly limited, and can be appropriately set according to the material of the surface of the bonded substrate, for example, the material of the conductive layer, the material of the outermost layer, the transfer speed, the press used, and the like. In the case where the transfer material has a cover film, the cover film may be removed and then pressure-bonded.
When the substrate is a resin film, the pressure bonding may be performed roll to roll.
The substrate used in the present invention is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface of a base material. The wiring is formed by patterning the conductive layer. In the present invention, a plurality of conductive layers of metal oxide, metal, or the like are preferably provided on a film substrate of polyethylene terephthalate or the like.
In addition, the substrate used in the present invention is preferably a substrate containing copper, from the viewpoint of further exhibiting the effects of the present invention. In addition, the conductive layer is preferably a layer containing copper, from the viewpoint of further exhibiting the effects of the present invention.
The substrate is preferably a substrate in which a plurality of conductive layers are stacked on a support.
In the substrate in which a plurality of conductive layers are stacked on a support, the support is preferably a glass substrate or a film substrate, and more preferably a film substrate. In the method for manufacturing a circuit wiring according to the present invention, the support is preferably a sheet-like resin composition particularly in the case of a circuit wiring for a touch panel.
The support is preferably transparent.
The refractive index of the support is preferably 1.50 to 1.52.
The support may be made of a light-transmitting substrate such as a glass substrate, and an strengthened glass typified by gorilla glass, which is a corning Incorporated co., ltd. As the transparent substrate, materials used in japanese patent application laid-open nos. 2010-086684, 2010-152809, and 2010-257492 can be preferably used.
When a film substrate is used as the substrate, a substrate that is not optically deformed and a substrate having high transparency are more preferably used, and specific materials include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.
The conductive layer may be any conductive layer used for a normal wiring or a touch panel wiring.
As a material of the conductive layer, a metal oxide, or the like can be exemplified.
Examples of the metal oxide include ITO (indium tin oxide), IZO (indium zinc oxide), and SiO2And the like. Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, and Mo.
In the method for manufacturing a resin pattern according to the present invention or the method for manufacturing a circuit wiring according to the present invention, it is preferable that at least one of the plurality of conductive layers contains a metal oxide.
The conductive layer is preferably an electrode pattern of a sensor corresponding to a visual recognition unit used in the capacitive touch panel or a wiring of a peripheral lead-out unit.
< Exposure Process >
The method for manufacturing a resin pattern according to the present invention or the method for manufacturing a circuit wiring according to the present invention preferably includes a step (exposure step) of pattern-exposing the photosensitive resin layer after the bonding step.
In the exposure step, the photosensitive resin layer is preferably irradiated with an activating light through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. The acid-decomposable group contained in the photosensitive resin layer is hydrolyzed by the catalytic action of the generated acid, and an acid group, for example, a carboxyl group or a phenolic hydroxyl group is generated.
In the present invention, the detailed arrangement and specific dimensions of the pattern are not particularly limited. In order to improve the display quality of a display device (for example, a touch panel) provided with an input device having a circuit board manufactured in the present invention and to reduce the area occupied by lead-out wirings as much as possible, at least a part of the pattern (particularly, an electrode pattern of the touch panel and a part of the lead-out wirings) is preferably a thin line of 100 μm or less, and more preferably a thin line of 70 μm or less.
The exposure in the exposure step may be exposure through a mask or digital exposure using a laser or the like, but is preferably exposure through an exposure mask.
The method for manufacturing a resin pattern according to the present invention or the method for manufacturing a circuit wiring according to the present invention preferably includes a step of bringing the transfer material into contact with an exposure mask between the bonding step and the exposure step. In this manner, the resolution of the obtained pattern is more excellent.
The activating light may, for example, be visible light, ultraviolet light or electron beam, preferably visible light or ultraviolet light, and particularly preferably ultraviolet light.
As the exposure light source by the activation light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a Light Emitting Diode (LED) light source, an excimer laser generator, and the like can be used, and the activation light having a wavelength of 300nm or more and 450nm or less such as g-ray (436nm), i-ray (365nm), h-ray (405nm), and the like can be preferably used. If necessary, the irradiation light can be adjusted by a spectral filter such as a long-wavelength cut filter, a short-wavelength cut filter, or a band-pass filter.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity device, a contact, a microlens array, and a laser exposure can be used.
The exposure amount may be appropriately selected depending on the photosensitive resin layer to be used, and is preferably 5mJ/cm2~200mJ/cm2More preferably 10mJ/cm2~100mJ/cm2
In addition, it is preferable to perform heat treatment before development in order to improve the rectangularity and linearity of the pattern after exposure. Roughness of the pattern edge due to standing waves generated in the photosensitive resin layer during Exposure can be reduced by a process called peb (post Exposure bake).
The pattern exposure may be performed after the temporary support is peeled from the photosensitive resin layer, or may be performed before the temporary support is peeled through the temporary support, and then the temporary support is peeled. The pattern exposure may be exposure through a mask, or may be digital exposure using a laser or the like.
< developing step >
The method for manufacturing a resin pattern according to the present invention or the method for manufacturing a circuit wiring according to the present invention preferably includes a step (developing step) of developing the exposed photosensitive resin layer to form a pattern after the exposure step.
In the case where the transfer material has an intermediate layer, the intermediate layer in the exposed portion is removed together with the exposed photosensitive resin layer in the developing step. Further, in the developing step, the intermediate layer in the unexposed portion may be removed in the form of being dissolved or dispersed in a developing solution.
The development of the exposed photosensitive resin layer in the developing step can be performed using a developer.
The developing solution is not particularly limited as long as the exposed portion of the photosensitive resin layer can be removed, and a known developing solution such as the developing solution described in japanese patent application laid-open No. 5-072724 can be used. The developing solution is preferably one in which the exposed portion of the photosensitive resin layer is subjected to a dissolving-type developing operation. The developer is preferably an aqueous alkaline solution, and more preferably an aqueous alkaline solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05mol/L (liter) to 5mol/L, for example. The developer may further contain an organic solvent miscible with water, a surfactant, and the like. As the developer preferably used in the present invention, for example, a developer described in section 0194 of international publication No. 2015/093271 can be mentioned.
The developing method is not particularly limited, and may be any of spin-on immersion development, shower and spin development, immersion development, and the like. Here, the shower development is detailed, and the exposed portion can be removed by spraying the developing solution onto the exposed photosensitive resin layer. After the development, the developer is preferably removed by spraying a cleaning agent or the like while wiping with a brush or the like. The temperature of the developing solution is preferably 20 ℃ to 40 ℃.
Further, the pattern shape of the present invention can be more effectively prevented from being deformed when the time from exposure to development is long. The development may be performed immediately after the exposure, but in the embodiment in which the development is performed after the lapse of a time period from the exposure to the development of preferably 0.5 hour or more, more preferably 1 hour or more, and further preferably 6 hours or more from the exposure, the effect of suppressing the deformation of the pattern shape in the present invention is more exhibited.
The method for producing a resin pattern according to the present invention or the method for producing a circuit wiring according to the present invention may include a known step such as a step of cleaning with water or the like after development, a step of drying a substrate having an obtained pattern, or the like.
Further, a post-baking step of heat-treating the pattern obtained by the development may be provided.
The post-baking is preferably heated in an environment of 8.1kPa to 121.6kPa, more preferably 50.66kPa or higher. On the other hand, it is more preferably carried out under an environment of 111.46kPa or less, and particularly preferably carried out under an environment of 101.3kPa or less.
The temperature of the postbaking is preferably from 80 ℃ to 250 ℃, more preferably from 110 ℃ to 170 ℃, and particularly preferably from 130 ℃ to 150 ℃.
The post-drying time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
The post-drying can be carried out in an air environment or a nitrogen replacement environment.
The transfer speed of the support body in each step in the method for producing a resin pattern according to the present invention or the method for producing a circuit wiring according to the present invention is not particularly limited, but is preferably 0.5m/min to 10m/min in the case of exposure removal, and more preferably 2.0m/min to 8.0m/min in the case of exposure removal.
< temporary support detachment step >
The method for manufacturing a resin pattern according to the present invention or the method for manufacturing a circuit wiring according to the present invention preferably includes a step of peeling off the temporary support (temporary support peeling step) after the step of bonding the resin pattern to the substrate and before the step of forming the pattern.
Since the method for producing a resin pattern according to the present invention or the method for producing a circuit wiring according to the present invention uses the transfer material, even if the temporary support is peeled off at any time after the transfer material is bonded and before development, the temporary support has excellent adhesion to the photosensitive resin layer, and therefore, occurrence of a failure such as partial peeling can be suppressed, and pattern formation can be performed satisfactorily.
In the method for manufacturing a resin pattern according to the present invention or the method for manufacturing a circuit wiring according to the present invention, it is more preferable that the method for manufacturing a resin pattern according to the present invention further includes a step of peeling off the temporary support after the step of bonding the resin pattern to the substrate and before the step of pattern-exposing the photosensitive resin layer, from the viewpoint of pattern formability and resolution. Further, in the above aspect, when pattern exposure is performed by contacting the mask, since the photosensitive resin layer does not directly contact the mask, pattern formability and resolution are further excellent.
The method for peeling off the temporary support in the peeling-off step is not particularly limited, and peeling off may be performed by a known method.
< cover film peeling step >
In the method for manufacturing a resin pattern according to the present invention or the method for manufacturing a circuit wiring according to the present invention, when the transfer material according to the present invention includes a cover film, it is preferable to include a step of peeling off the cover film of the transfer material (which may be referred to as a "cover film peeling step"). The method for peeling the cover film is not limited, and a known method can be applied.
< etching Process >
The method for manufacturing a circuit wiring according to the present invention preferably includes a step (etching step) of etching the conductive layer in a region where the pattern is not arranged.
In the etching step, the conductive layer is etched using the pattern formed by the photosensitive resin layer in the developing step as an etching resist.
The conductive layer can be etched by a known method such as the method described in, for example, paragraphs 0048 to 0054 of jp 2010-152155 a and the method of dry etching such as known plasma etching.
For example, the etching method may be wet etching in an etching solution, which is generally performed. The etching solution used in the wet etching may be an acidic type or an alkaline type, as appropriate, depending on the etching target.
Examples of the acidic etching solution include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxyfluor acid, oxalic acid, and phosphoric acid alone, and aqueous solutions of acidic components mixed with salts such as ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of a plurality of acidic components.
Examples of the alkaline type etching solution include an aqueous solution of an alkali component such as sodium hydroxide, potassium hydroxide, ammonia, or a salt of an organic amine such as an organic amine or tetramethylammonium hydroxide alone, and a mixed aqueous solution of an alkali component and a salt such as potassium permanganate. The alkali component may be a combination of a plurality of alkali components.
The temperature of the etching solution is not particularly limited, but is preferably 45 ℃ or lower. In the present invention, the pattern used as the etching mask (etching pattern) preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ℃ or lower. Therefore, the pattern is prevented from being peeled off in the etching step, and a portion where the pattern is not present is selectively etched.
After the etching step, in order to prevent contamination of the process line, a step of cleaning the etched substrate (cleaning step) and a step of drying the etched substrate (drying step) may be performed as necessary. The cleaning step includes, for example, cleaning the substrate with pure water at normal temperature (10 to 35 ℃) for 10 to 300 seconds. In the drying step, for example, the blowing pressure (0.1 kg/cm) is appropriately adjusted by blowing2~5kg/cm2(left and right)) And drying.
< etching resist stripping Process >
The method for manufacturing a circuit wiring according to the present invention preferably includes a step of peeling the photosensitive resin layer using a peeling liquid (etching resist peeling step) after the etching step.
After the etching step is completed, the photosensitive resin layer having a pattern remains. If the photosensitive resin layer is not necessary, all of the remaining photosensitive resin layer may be removed.
As a peeling method using a peeling liquid, for example, a method of immersing a substrate having the photosensitive resin layer or the like in a peeling liquid under stirring at preferably 30 to 80 ℃, more preferably 50 to 80 ℃ for 5 to 30 minutes can be exemplified.
Examples of the stripping solution include a solution obtained by dissolving an inorganic alkali component such as sodium hydroxide or potassium hydroxide, or an organic alkali component such as a tertiary amine or a quaternary ammonium salt in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. The peeling may be performed by a spray method, a shower method, a spin coating and dipping method, or the like using a peeling liquid.
In the method for manufacturing a circuit wiring according to the present invention, the exposure step, the development step, and the etching step may be repeated 2 or more times as necessary.
As examples of the exposure step, the development step, and other steps in the present invention, the methods described in paragraphs 0035 to 0051 of jp 2006-023696 can be preferably used in the present invention.
Full-face exposure of positive photosensitive resin layer to E
In the case where the photosensitive resin layer in the transfer material according to the present invention is a positive photosensitive resin layer, the method for manufacturing a circuit wiring according to the present invention preferably includes, after the etching step, a step of subjecting the positive photosensitive resin layer to full-surface exposure (hereinafter, may be referred to as "full-surface exposure step"), and a step of removing the full-surface exposed positive photosensitive resin layer.
In a conventional circuit wiring manufacturing method, when a removing solution for an etching mask is used for a long time, the removing property of the etching mask may be gradually lowered. By exposing the positive photosensitive resin layer used as an etching mask to light over the entire surface after the etching step, the solubility in the removing solution and the permeability of the removing solution are improved, and the removing solution is excellent in the removability even when used for a long time.
The above-described method for manufacturing a circuit wiring can be repeatedly applied to a substrate having a base material and a plurality of conductive layers including a first conductive layer and a second conductive layer having different structural materials, thereby manufacturing a circuit wiring.
The step of peeling the positive photosensitive resin layer exposed over the entire surface can be performed in the same manner as in the etching resist peeling step.
< Whole surface Exposure step >
In the entire surface exposure step, all of the positive photosensitive resin layer of the residual image may be exposed by development, and the exposure may be performed or not performed on the portion where the positive photosensitive resin layer is not present. From the viewpoint of simplicity, for example, it is preferable to expose the entire surface of the substrate on the side having the positive photosensitive resin layer.
The light source used for exposure in the entire surface exposure step is not particularly limited, and a known exposure light source can be used. From the viewpoint of removability, it is preferable to use a light source containing light having the same wavelength as that in the exposure step.
From the viewpoint of removability, the exposure amount in the whole surface exposure step is preferably 5mJ/cm2~1,000mJ/cm2More preferably 10mJ/cm2~800mJ/cm2Particularly preferably 100mJ/cm2~500mJ/cm2
From the viewpoint of removability, the exposure amount in the entire surface exposure step is preferably equal to or greater than the exposure amount in the exposure step, and more preferably greater than the exposure amount in the exposure step.
< heating step >
The method for manufacturing a circuit wiring according to the present invention may include a step of heating the positive photosensitive resin layer exposed over the entire surface (hereinafter, may be referred to as a "heating step") during the entire surface exposure step, after the exposure step, or both, and before a removal step described later. By including the heating step, the reaction rate of the photo-acid generator and the reaction rate of the generated acid with the positive photosensitive resin can be further increased, and as a result, the removal performance is improved.
The method for manufacturing a resin pattern according to the present invention or the method for manufacturing a circuit wiring according to the present invention may include other arbitrary steps. For example, the following steps may be mentioned, but the present invention is not limited to these steps.
< step of reducing reflectance of visible ray >
The method for manufacturing a circuit wiring according to the present invention may include the steps of: the visible ray reflectance of the surface of the conductive layer, for example, a part or the entire surface of the conductive layer provided on the substrate, is reduced.
The treatment for reducing the visible light reflectance may, for example, be an oxidation treatment. For example, the visible light reflectance can be reduced by oxidizing copper to form copper oxide and blackening the copper oxide.
Preferable modes of the treatment for reducing the reflectance of visible rays are described in paragraphs 0017 to 0025 of Japanese patent laid-open publication No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese patent laid-open publication No. 2013-206315, the contents of which are incorporated in the present specification.
< Process for Forming insulating film on etched substrate and Process for Forming New conductive layer on insulating film >
The method for manufacturing a circuit wiring according to the present invention preferably includes a step of forming an insulating film on the substrate, for example, on the formed wiring (etched conductive layer), and a step of forming a new conductive layer on the insulating film.
The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be exemplified. Further, an insulating film having a desired pattern can be formed by photolithography using an insulating photosensitive material.
The step of forming a new conductive layer on the insulating film is not particularly limited. A new conductive layer having a desired pattern can be formed by photolithography using a photosensitive material having conductivity.
In the method for manufacturing a circuit wiring according to the present invention, the new conductive layer may be etched by forming an etching resist in the same manner as described above, or may be separately etched by a known method.
The substrate having circuit wiring obtained by the method for manufacturing circuit wiring according to the present invention may have only one layer of wiring on the substrate, or may have two or more layers of wiring.
In the method for manufacturing a circuit wiring according to the present invention, it is also preferable that the substrate has a plurality of conductive layers on both surfaces thereof, and that the circuit is formed on the conductive layers formed on both surfaces of the substrate sequentially or simultaneously. With this configuration, the first conductive pattern (first wiring) can be formed on one surface of the substrate, and the second conductive pattern (second wiring) can be formed on the other surface, and preferably, the wiring for a touch panel can be formed.
Volume to volume mode
The method for manufacturing a resin pattern according to the present invention or the method for manufacturing a circuit wiring according to the present invention is preferably performed by a roll-to-roll method.
The roll-to-roll method is as follows: the substrate that can be wound up and unwound is used as a substrate, and includes a step of winding up the substrate or a structure including the substrate before any step included in a circuit wiring manufacturing method (hereinafter, sometimes referred to as a "winding-up step"), and a step of winding up the substrate or the structure including the substrate after any step (hereinafter, sometimes referred to as a "winding-up step"), and at least any step (preferably all steps except for all steps or a heating step) is performed while conveying the substrate or the structure including the substrate.
The winding-out method in the winding-out step and the winding-up method in the winding-up step are not particularly limited, and a known method may be used in a manufacturing method to which the roll-to-roll method is applied.
The circuit wiring according to the present invention is a circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention.
The substrate having the circuit wiring according to the present invention is a substrate having a circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention.
The application of the substrate having the circuit wiring according to the present invention is not limited, and for example, a circuit wiring substrate for a touch panel is preferable.
The input device may be an input device as an example of a device including the circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention.
The input device according to the present invention may be an input device having at least the circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present invention, and is preferably a touch panel, and more preferably an electrostatic capacitance type touch panel.
The display device according to the present invention preferably includes the input device according to the present invention. The display device according to the present invention is preferably an image display device such as an organic EL display device or a liquid crystal display device.
(method of manufacturing touch Panel)
The method for manufacturing a touch panel according to the present invention is not particularly limited as long as it is a method for manufacturing a touch panel using the transfer material according to the present invention, and the method preferably includes, in order: a step of bonding an outermost layer of the transfer material on the side having the positive photosensitive resin layer with respect to the temporary support to a substrate having a conductive layer (hereinafter, may be referred to as a "bonding step"); a step of pattern-exposing the positive photosensitive resin layer of the transfer material after the bonding step (hereinafter, may be referred to as an "exposure step"); a step of forming a resin pattern by developing the positive photosensitive resin layer after the pattern exposure step (hereinafter, may be referred to as a "developing step"); and a step of etching the substrate in a region where the resin pattern is not arranged (hereinafter, may be referred to as "etching step").
The method of manufacturing a touch panel according to the present invention preferably includes a step of peeling off the temporary support (temporary support peeling step) after the bonding step and before the developing step.
The method of manufacturing a touch panel according to the present invention may further include a step of peeling off the cover film of the transfer material (cover film peeling step) before the bonding step.
As for the specific embodiments of the respective steps of the temporary support peeling step, the bonding step, the exposure step, the development step, the etching step, and the cover film peeling step in the method for manufacturing a touch panel according to the present invention, as described in the section of "method for manufacturing circuit wiring", the preferable embodiments are also the same.
The touch panel according to the present invention is a touch panel including at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present invention. The touch panel according to the present invention preferably includes at least a transparent substrate, an electrode, an insulating layer, or a protective layer.
The detection method in the touch panel according to the present invention may be any of known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the electrostatic capacitance system is preferable.
Examples of the Touch panel type include a so-called embedded type (described in, for example, fig. 5, 6, 7, and 8 of japanese laid-open patent publication No. 2012-517051), a so-called external embedded type (described in, for example, fig. 19 of japanese laid-open patent publication No. 2013-168125, fig. 1 and 5 of japanese laid-open patent publication No. 2012-089102), an OGS (One Glass Solution: One-piece Glass Touch technology) type, a TOL (Touch-on-Lens) type (described in, for example, fig. 2 of japanese laid-open patent publication No. 2013-054727), other structures (described in, for example, fig. 6 of japanese laid-open patent publication No. 2013-164871), and various external hanging types (described in, for example, GG, G1-G2, GFF, GF2, GF1, G1F, and the like).
The touch panel according to the present invention may be a touch panel described in paragraph 0229 of japanese patent application laid-open No. 2017-120345.
Examples
The following examples are intended to more specifically describe the embodiments of the present invention. The materials, the amounts used, the ratios, the contents of the processes, the process procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the embodiment of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.
[ Polymer in Positive photosensitive resin layer ]
In the following examples, the following abbreviations respectively represent the following compounds.
ATHF: acrylic acid 2-tetrahydrofurfuryl ester (synthetic product)
MATHF: 2-tetrahydrofurfuryl methacrylate (synthetic)
AA: acrylic acid (Tokyo Chemical Industry Co., Ltd.)
MMA: methyl methacrylate (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)
EA: ethyl acrylate (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)
CHA: cyclohexyl acrylate (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)
PGMEA (propylene glycol monomethyl ether acetate): (SHOWA DENKO K.K. system)
V-601: dimethyl-2, 2' -azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
< Synthesis of ATHF >
The synthesis was carried out according to the method described in paragraph 0166 of International publication No. 2018/179640.
< Synthesis of MATHF >
The synthesis was carried out according to the method described in paragraph 0167 of International publication No. 2018/179640.
< example for Synthesis of Polymer A-1 >
PGMEA (75.0 parts) was added to a three-necked flask, and the temperature was raised to 90 ℃ under a nitrogen atmosphere. A solution to which ATHF (30.0 parts), MMA (35.0 parts), EA (35.0 parts), V-601(4.0 parts) and PGMEA (75.0 parts) were added was added dropwise over 2 hours to a three-necked flask solution maintained at 90 ℃. + -. 2 ℃. After the end of the dropwise addition, the mixture was stirred at 90 ℃. + -. 2 ℃ for 2 hours, whereby polymer A-1 (solid content concentration 40.0%) was obtained. Tg was 35 ℃ and the weight average molecular weight (Mw) was 35,000.
< example for Synthesis of Polymer A-2 >
Monomers were changed to MATHF (40.0 parts), AA (3.0 parts) and CHA (57.0 parts), and synthesis was performed under the same conditions as those for A-1. The solid content concentration of the polymer was 40 mass%. Tg of 48 ℃ and a weight average molecular weight (Mw) of 25,000.
< example for Synthesis of Polymer A-3 >
According to the method described in section 0232 of Japanese patent laid-open No. 2014-085643, a polymer A-3 (PHS-EVE, weight average molecular weight: 20,000, having the following structure) was obtained. In the following structures, the numerical value of each structural unit represents the content (mass%) of each structural unit.
[ chemical formula 5]
Figure BDA0003069266620000431
[ photoacid generators ]
B-1: irgacure PAG-103 manufactured by BASF corporation, the following compound
[ chemical formula 6]
Figure BDA0003069266620000441
B-2: a compound having a structure shown below (a compound described in paragraph 0227 of Japanese patent laid-open publication No. 2013-047765, which was synthesized according to the method described in paragraph 0227.)
[ chemical formula 7]
Figure BDA0003069266620000442
[ surfactant ]
E-1: a compound of the structure shown below
[ chemical formula 8]
Figure BDA0003069266620000443
[ basic Compound ]
D-1: N-cyclohexyl-N' - [2- (4-morpholinyl) ethyl ] thiourea (New chemical tracing co., Ltd., product No.: CMTU)
< preparation of photosensitive resin composition 1>
A photosensitive resin composition 1 was obtained by blending the following components and filtering the mixture with a polytetrafluoroethylene filter having a pore size of 0.2. mu.m.
[ composition of photosensitive resin composition 1]
PGMEA: 424.5 parts by mass
Polymer A-1: 237.0 parts by mass
Photoacid generator B-2: 5.0 parts by mass
Surfactant E-1: 0.1 part by mass
Basic compound D-1: 0.1 part by mass
< preparation of composition for Forming intermediate layer 1>
The components were mixed in the following composition to prepare an intermediate layer-forming composition 1.
[ composition of composition 1 for intermediate layer formation ]
Pure water: 33.7 parts by mass
Methanol: 61.2 parts by mass
Hydroxypropyl cellulose (HPC, NIPPON SODA co., ltd. manufactured HPC-SSL): 5.0 parts by mass
MegafacF-569(F-569, non-ionic surfactant (oligomer) having a fluorine atom, manufactured by DIC corporation, having a molecular weight of 700 or more): 0.1 part by mass
[ preparation of compositions 2 to 16 for Forming intermediate layer ]
Intermediate layer-forming compositions 2 to 16 were prepared in the same manner as in the preparation of intermediate layer-forming composition 1 except that the kinds of water-soluble resin and surfactant and the amount of surfactant added in intermediate layer-forming composition 1 were changed as described in table 1 below.
[ Table 1]
Figure BDA0003069266620000461
The surfactants described in table 1 were dissolved in 100g of distilled water at 25 ℃ by 1.0g or more.
The abbreviations in table 1 other than the above are shown in the following in detail.
HPMC: hydroxypropyl methylcellulose, Shin-Etsu chemical co., Ltd, TC-5E Low molecular weight type
F-114: MegafacF-114, manufactured by DIC corporation, an anionic surfactant having a perfluoroalkyl group and a sulfonic acid group, and does not contain an anionic surfactant having a molecular weight of 700 or more.
F-410: MegafacF-410, manufactured by DIC corporation, an anionic surfactant having a perfluoroalkyl group and a carboxyl group, and does not contain an anionic surfactant having a molecular weight of 700 or more.
F-444: MegafacF-444, produced by DIC corporation, a nonionic surfactant having a perfluoroalkyl group and an alkyleneoxy group, and does not contain a surfactant having a molecular weight of 700 or more.
F-477: MegafacF-477, DIC corporation, a nonionic surfactant (oligomer) having a fluorine atom, and having a molecular weight of 700 or more.
F-510: MegafacF-510, manufactured by DIC corporation, an anionic surfactant (oligomer) having a perfluoroalkyl group and a phosphoric acid group, and having a molecular weight of 700 or more.
F-553: MegafacF-553, DIC corporation, a nonionic surfactant (oligomer) having a fluorine atom, and having a molecular weight of 700 or more.
F-556: MegafacF-556, DIC corporation, a nonionic surfactant (oligomer) having a fluorine atom, and having a molecular weight of 700 or more.
F-559: MegafacF-556, DIC corporation, a nonionic surfactant (oligomer) having a fluorine atom, and having a molecular weight of 700 or more.
R-94: MegafacR-94, DIC corporation, a nonionic surfactant (oligomer) having a fluorine atom, and having a molecular weight of 700 or more.
(example 1)
< preparation of transfer Material >
The intermediate layer-forming composition 1 was applied to a polyethylene terephthalate (PET) film (temporary support, thickness 25 μm) using a slit nozzle in such an amount that the dry film thickness became 1.6 μm. After the drying of the composition 1 for forming an intermediate layer, the composition 1 for forming an intermediate layer was further applied thereon again in an amount of 0.4 μm using a slit nozzle.
After the intermediate layer-forming composition 1 was dried, the photosensitive resin composition 1 was applied thereon in an amount such that the dry film thickness became 3.0 μm.
Thereafter, the film was dried with warm air at 100 ℃, and finally, a polyethylene film (OSM-N, manufactured by Tredegar Corporation) was pressure-bonded as a cover film to prepare a transfer material (photosensitive transfer material) of example 1.
(examples 2 to 14)
Transfer materials of examples 2 to 14 were produced in the same manner as in example 1 except that the intermediate layer forming composition 1 was changed to the intermediate layer forming compositions 2 to 14, respectively.
(example 15)
The intermediate layer-forming composition 4 was applied to a PET film (temporary support, thickness 25 μm) using a slit nozzle in such an amount that the dry film thickness became 1.6 μm. After the drying of the composition 4 for forming an intermediate layer, the composition 15 for forming an intermediate layer was further applied thereto again in an amount of 0.4 μm using a slit nozzle.
After the intermediate layer-forming composition 15 was dried, the photosensitive resin composition 1 was applied thereon in an amount such that the dry film thickness became 3.0 μm.
Thereafter, the transfer material of example 15 was prepared by drying the film with warm air at 100 ℃ and finally pressure-bonding a polyethylene film (OSM-N, manufactured by Tredegar Corporation) as a cover film.
(example 16)
A transfer material of example 16 was produced in the same manner as in example 1 except that the photosensitive resin composition 1 was coated in such an amount that the dry film thickness thereof became 5.0. mu.m.
(examples 17 and 18)
A transfer material of example 17 or example 18 was produced in the same manner as in example 1 except that the photosensitive resin composition 1 was changed to the photosensitive resin composition 2 or the photosensitive resin composition 3.
< production of photosensitive resin compositions 2 and 3>
Photosensitive resin compositions 2 and 3 were obtained by mixing them with the following composition and filtering them with a polytetrafluoroethylene filter having a pore size of 0.2 μm.
[ composition of photosensitive resin composition 2]
PGMEA: 424.5 parts by mass
Polymer A-2: 237.0 parts by mass
Photoacid generator B-2: 5.0 parts by mass
Surfactant E-1: 0.1 part by mass
Basic compound D-1: 0.1 part by mass
[ composition of photosensitive resin composition 3]
P6 MEA: 424.5 parts by mass
Polymer A-3: 237.0 parts by mass
Photoacid generator B-1: 5.0 parts by mass
Surfactant E-1: 0.1 part by mass
Basic compound D-1: 0.1 part by mass
(example 19)
< preparation of transfer Material >
The intermediate layer-forming composition 1 was applied to PET using a slit nozzle in such an amount that the dry film thickness became 1.6 μm.
After the intermediate layer-forming composition 1 was dried, the photosensitive resin composition 1 was applied thereon in an amount such that the dry film thickness became 3.0 μm.
Thereafter, the transfer material of example 19 was prepared by drying the film with warm air at 100 ℃ and, finally, pressure-bonding a polyethylene film (OSM-N, manufactured by Tredegar Corporation) as a cover film.
Comparative example 1
A transfer material of comparative example 1 was produced in the same manner as in example 1, except that the intermediate layer forming composition 1 was changed to the intermediate layer forming composition 16.
< evaluation of streaks >
The coating film was peeled off from the prepared transfer material, and the transfer material was irradiated with light from a fluorescent lamp, and the appearance of streaks was visually evaluated from an oblique angle of 45 °. The "streaks" in the transfer material according to the present invention indicate a failure in which streaky irregularities occur on the surface of the transfer material to be transferred (the transfer surface, which is the surface of the photosensitive resin layer of the release coating film in the above examples and comparative examples). The streaks are often generated parallel to the transport direction of the transfer material during production. If such streaks occur, bubbles often enter the streaks during transfer, and there is a high possibility that a large number of wiring defects occur when defects (such as missing patterns and pattern collapse) in the pattern shape and when the transfer material is used as an etching resist for producing circuit wiring.
Preferably A or B, more preferably A.
Evaluation criteria-
A: no streaks were observed at a distance of 15cm or 40 cm.
B: no streaks were observed from a distance of 40cm, but streaks were observed from a distance of 15 cm.
C: the streaks were clearly observed from either a distance of 15cm or a distance of 40 cm.
< evaluation of Wiring Defect >
Production of the substrate
A roll substrate (PET substrate with a copper layer) was prepared by forming a copper layer on a polyethylene terephthalate (PET) film having a thickness of 200 μm by sputtering at a thickness of 250 nm.
Evaluation of wiring defects-
The cover film was peeled from the transfer material thus prepared, and the resultant was laminated on a PET substrate with a copper layer under lamination conditions of a lamination roll temperature of 100 ℃, a linear pressure of 0.6MPa, and a linear velocity (lamination velocity) of 4.0 m/min. A line-and-space pattern (Duty ratio 1: 1) mask having a line width of 6 μm was brought into contact with a temporary support, exposed to an ultra-high pressure mercury lamp, and then left at 23 ℃ for 3 hours and developed. Development was carried out for 40 seconds by shower development using a 1.0 mass% aqueous sodium carbonate solution at 28 ℃. A line-and-space pattern having a line width of 6 μm was formed by the above method, and the exposure amount at which the ratio of the line width to the space width became 1: 1 was obtained. A line and space pattern having a line width of 6 μm at the exposure was formed by the above method, and the pattern was etched by immersion in a copper etching solution (Cu-02, KANTO CHEMICAL co., inc., product) at 25 ℃ for 5 minutes to prepare a square copper pattern wiring. The obtained copper pattern wiring was observed with an optical microscope. The number of wiring defects of the copper pattern wiring in five frames in total was measured in the center portion of the copper pattern wiring and the four corners of the square shape with the observation area of 0.26mm × 0.20mm in the copper pattern wiring as one frame. The following evaluation was performed based on the maximum number of combinations of wiring defects due to disconnection (head) of wirings and coupling (short-circuiting) of wirings in one frame in five frames. Preferably A or B.
A: defects of the copper pattern were not recognized completely visually.
B: the number of defects in the copper pattern is one or more and four or less.
C: the number of defects in the copper pattern is five or more.
< evaluation of adhesion >
The cover film was peeled from the transfer material thus prepared, and the resultant was laminated on the PET substrate with the copper layer under lamination conditions of a lamination roll temperature of 100 ℃, a linear pressure of 0.6MPa, and a linear speed (lamination speed) of 4.0 m/min. Subsequently, the sample was cut into 4.5cm × 10cm, and the PET substrate side with the copper layer was fixed on a sample table.
The PET substrate with the copper layer was stretched at 5.5 mm/sec in a direction of 180 degrees by using a tensile compression tester (SV-55 manufactured by IMADA-SS Corporation), and the interlayer and the temporary support were peeled off to measure the adhesion force.
The measured adhesion force (N/cm) was used as an index of adhesion and evaluated according to the following evaluation criteria. The adhesion can be said to be more excellent as the adhesion force is larger. The evaluation results are set forth in table 2.
Evaluation criteria-
A: the adhesive force exceeds 0.098N/cm.
B: the adhesive force is 0.069N/cm-0.098N/cm.
C: the adhesive force is less than 0.069N/cm.
[ Table 2]
Figure BDA0003069266620000511
As is clear from Table 2, the transfer materials of examples 1 to 19 had fewer streaks on the surface to be transferred than the transfer material of comparative example 1.
Further, according to the above table 2, the transfer materials of examples 1 to 19 were also excellent in adhesion during transfer, and wiring defects were also reduced when the transfer materials were used as etching resists.
(example 101)
ITO was formed on a 100 μm thick PET substrate by sputtering to a thickness of 150nm as a second conductive layer, and copper was formed thereon by vacuum deposition to a thickness of 200nm as a first conductive layer to form a circuit forming substrate.
The transfer material obtained in example 1 was bonded to a substrate (laminating roller temperature 100 ℃, linear pressure 0.8MPa, linear speed 3.0m/min.) on the copper layer to obtain a laminate. The obtained laminate was exposed to a contact pattern having a structure in which conductive layer pads are connected in one direction without peeling the temporary support, using a photomask provided with a pattern (hereinafter, also referred to as "pattern a") shown in fig. 2.
In the pattern a shown in fig. 2, the solid line portion SL and the gray line portion G are light-shielding portions, and the dotted line portion DL virtually shows an alignment frame.
After that, the temporary support was peeled off, and development and water washing were performed to obtain a pattern a. Next, after the copper layer was etched using a copper etching solution (KANTO CHEMICAL co., manufactured by inc., product Cu-02), the ITO layer was etched using an ITO etching solution (KANTO CHEMICAL co., manufactured by inc., product ITO-02), thereby obtaining a substrate in which both copper and ITO were drawn using the pattern a.
Next, in the aligned state, pattern exposure was performed using a photomask provided with an opening of the pattern shown in fig. 3 (hereinafter, also referred to as "pattern B"), and development and water washing were performed.
In the pattern B shown in fig. 3, the gray portion G is a light shielding portion, and the dotted line portion DL virtually shows an alignment frame.
Thereafter, the copper layer was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a peeling liquid (KANTO CHEMICAL co., inc.
The obtained circuit wiring board was observed with a microscope, and was a perfect pattern without peeling, chipping, or the like.
(example 102)
An ITO layer was formed on a 100 μm thick PET substrate by sputtering to a thickness of 150nm as a second conductive layer, and a copper layer was formed thereon by vacuum deposition to a thickness of 200nm as a first conductive layer to form a circuit forming substrate.
The transfer material obtained in example 1 was bonded to a substrate (laminating roller temperature 100 ℃, linear pressure 0.8MPa, linear speed 3.0m/min.) on the copper layer to obtain a laminate. The obtained laminate was subjected to pattern exposure using a photomask provided with a pattern a having a structure in which the temporary support was not peeled off and the conductive layer pads were connected in one direction. After that, the temporary support was peeled off, and development and water washing were performed to obtain a pattern a. Next, after the copper layer was etched using a copper etching solution (KANTO CHEMICAL co., product of inc., Cu-02), the ITO layer was etched using an IT0 etching solution (KANTO CHEMICAL co., product of inc., IT0-02), thereby obtaining a substrate in which both copper and ITO were drawn with pattern a.
Subsequently, pet (a) was laminated on the remaining resist as a protective layer. In this state, pattern exposure was performed using a photomask having an opening of the pattern B in an aligned state, and after peeling pet (a), development and washing were performed. Thereafter, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a peeling liquid (KANTO CHEMICAL co., inc. product KP-301), thereby obtaining a circuit wiring board.
The obtained circuit wiring board was observed with a microscope, and was a perfect pattern without peeling, chipping, or the like.
(example 103)
An ITO conductive layer as a second layer was formed on a 100 μm thick cycloolefin polymer (COP) substrate by sputtering to a thickness of 150nm, and a conductive layer as a first layer of copper was formed thereon by vacuum deposition to a thickness of 200nm as a substrate for forming a conductive pattern.
The transfer material obtained in example 1 was bonded to a substrate (laminating roller temperature 100 ℃, linear pressure 0.8MPa, linear speed 3.0m/min.) on the copper layer to obtain a laminate. The obtained laminate was subjected to pattern exposure using a photomask provided with a pattern a having a structure in which the temporary support was not peeled off and the conductive layer pads were connected in one direction. After that, the temporary support is peeled off, and development and water washing are performed to obtain a resin pattern drawn by the pattern a. Next, after etching the copper layer using a copper etching solution (KANTO CHEMICAL co., inc. CU-02), the IT0 layer was etched using an ITO etching solution (KANTO CHEMICAL co., inc. ITO-02), and the substrate on which both copper and IT0 were drawn using pattern a was obtained by peeling using a peeling solution (KANTO CHEMICAL co., inc. KP-301).
Next, the transfer material obtained in example 1 was bonded to the remaining resist (roll temperature 100 ℃, linear pressure 0.8MPa, linear velocity 3.0 m/min.). In this state, pattern exposure is performed using a photomask having an opening of the pattern B in an aligned state, and after the temporary support of the transfer material is peeled, development and water washing are performed. Thereafter, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a peeling liquid (KANTO CHEMICAL co., inc. product KP-301), thereby obtaining a circuit wiring board having a conductive pattern.
The obtained circuit wiring board was observed with a microscope, and was a perfect pattern without peeling, chipping, and the like.
The disclosure of japanese patent application No. 2018-217753, filed on 11/20/2018, the entire contents of which are incorporated herein by reference.
All documents, patent applications, and technical standards described in the present specification are incorporated by reference into the present specification to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.
Description of the symbols
10-temporary support, 12-intermediate layer, 14-photosensitive resin layer, 16-cover film, 100-transfer material, SL-solid line portion, G-gray portion, DL-dotted line portion.

Claims (12)

1. A transfer material having, in order:
a temporary support;
an intermediate layer comprising a water-soluble resin; and
a positive type photosensitive resin layer,
the intermediate layer contains a surfactant having a fluorine atom.
2. The transfer material according to claim 1,
the surfactant comprises a compound having a molecular weight of 700 or more.
3. The transfer material according to claim 1 or 2,
the surfactant has a solubility of 1g or more relative to 100g of water at 25 ℃.
4. The transfer material according to any one of claims 1 to 3,
the content of the surfactant is 0.1 to 1.0 mass% with respect to the total mass of the intermediate layer.
5. The transfer material according to any one of claims 1 to 4,
the surfactant is a surfactant having a fluoroalkyl group and an alkyleneoxy group.
6. The transfer material according to any one of claims 1 to 5,
the surfactant is a surfactant having a perfluoroalkyl group and a polyalkyleneoxy group.
7. The transfer material according to any one of claims 1 to 6,
the content of the polymer component in the positive photosensitive resin layer is 75 mass% or more with respect to the total mass of the positive photosensitive resin layer.
8. The transfer material according to any one of claims 1 to 7,
the positive photosensitive resin layer contains a polymer and a photoacid generator, and the polymer contains a structural unit having an acid group protected by an acid-decomposable group.
9. The transfer material according to claim 8,
the structural unit having an acid group protected by an acid-decomposable group is a structural unit represented by any one of the following formulae A1 to A3,
Figure FDA0003069266610000021
in the formula A1, R11And R12Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R11And R12Any of which is alkyl or aryl, R13Represents alkyl or aryl, optionally R11Or R12And R13Linked to form a cyclic ether, R14Represents a hydrogen atom or a methyl group, X1Represents a single bond or a divalent linking group, R15Represents a substituent, n represents an integer of 0 to 4,
in the formula A2, R21And R22Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R21And R22Any of which is alkyl or aryl, R23Represents alkyl or aryl, optionally R21Or R22And R23Linked to form a cyclic ether, R24Each independently represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, m represents an integer of 0 to 3,
in the formula A3, R31And R32Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R31And R32Any of which is alkyl or aryl, R33Represents alkyl or aryl, optionally R31Or R32And R33Linked to form a cyclic ether, R34Represents a hydrogen atom or a methyl group, X0Represents a single bond or a divalent linking group.
10. A method of manufacturing a resin pattern, comprising in order:
a step of bringing an outermost layer on the side having the positive photosensitive resin layer with respect to the temporary support in the transfer material according to any one of claims 1 to 9 into contact with a substrate and bonding the outermost layer to the substrate;
a step of pattern-exposing the positive photosensitive resin layer; and
and forming a resin pattern by developing the exposed positive photosensitive resin layer.
11. A method of manufacturing a circuit wiring, comprising in order:
a step of bringing an outermost layer on the side having the positive photosensitive resin layer with respect to the temporary support in the transfer material according to any one of claims 1 to 9 into contact with a substrate having a conductive layer and bonding the outermost layer to the substrate;
a step of pattern-exposing the positive photosensitive resin layer;
a step of forming a resin pattern by developing the exposed positive photosensitive resin layer; and
and etching the conductive layer in a region where the resin pattern is not disposed.
12. A method of manufacturing a touch panel, comprising in order:
a step of bringing an outermost layer on the side having the positive photosensitive resin layer with respect to the temporary support in the transfer material according to any one of claims 1 to 9 into contact with a substrate having a conductive layer and bonding the outermost layer to the substrate;
a step of pattern-exposing the positive photosensitive resin layer;
a step of forming a resin pattern by developing the exposed positive photosensitive resin layer; and
and etching the conductive layer in a region where the resin pattern is not disposed.
CN201980075793.4A 2018-11-20 2019-11-07 Transfer material, method for manufacturing resin pattern, method for manufacturing circuit wiring, and method for manufacturing touch panel Pending CN113056373A (en)

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