WO2019225363A1 - Matériau de transfert photosensible, procédé de production de motif de résine, procédé de fabrication de câblage de circuit, et procédé de fabrication de panneau tactile - Google Patents

Matériau de transfert photosensible, procédé de production de motif de résine, procédé de fabrication de câblage de circuit, et procédé de fabrication de panneau tactile Download PDF

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WO2019225363A1
WO2019225363A1 PCT/JP2019/018815 JP2019018815W WO2019225363A1 WO 2019225363 A1 WO2019225363 A1 WO 2019225363A1 JP 2019018815 W JP2019018815 W JP 2019018815W WO 2019225363 A1 WO2019225363 A1 WO 2019225363A1
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group
polymer
structural unit
mass
photosensitive resin
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PCT/JP2019/018815
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English (en)
Japanese (ja)
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知樹 松田
一真 両角
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富士フイルム株式会社
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Priority to CN201980034383.5A priority Critical patent/CN112166377A/zh
Priority to JP2020521157A priority patent/JPWO2019225363A1/ja
Publication of WO2019225363A1 publication Critical patent/WO2019225363A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

Definitions

  • the present disclosure relates to a photosensitive transfer material, a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method.
  • a display device such as an organic electroluminescence (EL) display device and a liquid crystal display device
  • a touch panel such as a capacitance type input device
  • an electrode pattern corresponding to a sensor of a visual recognition part a wiring of a peripheral wiring part
  • a lead-out wiring part A conductive layer pattern such as is provided inside the touch panel.
  • a patterned layer is formed by a photosensitive resin composition layer provided on an arbitrary substrate using a photosensitive transfer material because the number of steps for obtaining a required pattern shape is small.
  • a method of developing after exposure through a mask having a desired pattern is widely used.
  • Patent Document 1 includes a temporary support, a polymer having a structural unit represented by the following general formula A and a structural unit having an acid group, and having a glass transition temperature of 90 ° C. or lower, and a photoacid generator. There is disclosed a photosensitive transfer material having a positive photosensitive resin layer containing.
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group. Alternatively, it represents an aryl group, and R 31 or R 32 and R 33 may be linked to form a cyclic ether.
  • R 34 represents a hydrogen atom or a methyl group
  • X 0 represents a single bond or an arylene group.
  • Patent Document 2 what was described in patent document 2 is known as a conventional photosensitive resin composition.
  • A a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, which increases the solubility in an alkali developer by the action of an acid, and
  • B an acid is generated by irradiation with actinic rays or radiation.
  • a positive resist composition for immersion exposure comprising (C) an alkali-soluble compound having an alkyl group having 5 or more carbon atoms, and (D) a solvent.
  • Patent Document 1 Japanese Patent Laid-Open No. 2017-156735
  • Patent Document 2 Japanese Patent Laid-Open No. 2006-48029
  • the problem to be solved by one embodiment of the present invention is to provide a photosensitive transfer material that is excellent in surface shape and excellent in dimple suppression of the resulting pattern.
  • Another problem to be solved by another embodiment of the present invention is to provide a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method using the photosensitive transfer material. .
  • Means for solving the above problems include the following aspects. ⁇ 1> A polymer A having a temporary support and a photosensitive resin layer, wherein the photosensitive resin layer includes a structural unit having an acid group protected with an acid-decomposable group, a photoacid generator, and And the polymer F containing a structural unit having a fluorine atom, and the fluorine atom content in the polymer F is 20% by mass or more and 50% by mass or less with respect to the total mass of the polymer F.
  • f1 The I / O value of the polymer F is 0.45 or more.
  • the polymer F has an I / O value of less than 0.45, and the polymer F includes a structural unit having an acid group or a basic group.
  • the polymer F is at least selected from the group consisting of a hydroxy group, an ether bond, a thioether bond, a carbonyl group, an amide structure, a lactone structure, a thioester bond, a urea bond, a thiourea bond, a urethane bond, and a cyano group.
  • the photosensitive transfer material according to ⁇ 1> comprising a structural unit having one type of structure in the side chain.
  • ⁇ 3> The photosensitive transfer material according to ⁇ 1> or ⁇ 2>, wherein the polymer F satisfies the above f2.
  • ⁇ 4> The photosensitive transfer material according to ⁇ 3>, wherein the polymer F includes a structural unit having a carboxy group as the structural unit having the acid group.
  • the content of the polymer F is any one of ⁇ 1> to ⁇ 4>, in which the content is 0.01% by mass to 1% by mass with respect to the total mass of the photosensitive resin layer.
  • Photosensitive transfer material. ⁇ 6> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 5>, wherein the polymer F has a glass transition temperature of 50 ° C. or lower.
  • ⁇ 7> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 6>, wherein the acid value of the polymer A is 0.5 mmol / g or less.
  • ⁇ 8> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 7>, wherein the polymer A has an I / O value of 0.65 or less.
  • ⁇ 9> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 8>, wherein the structural unit having an acid group protected with an acid-decomposable group is a structural unit represented by the following formula A: .
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group or Represents an aryl group, and R 31 or R 32 and R 33 may combine to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or a divalent linking group. Represents.
  • ⁇ 10> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 9>, wherein the photoacid generator is a photoacid generator that generates sulfonic acid.
  • the step of bringing the outermost layer on the photosensitive resin layer side of the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 10> into contact with a substrate and bonding the photosensitive resin layer, and patterning the photosensitive resin layer A method for producing a resin pattern, comprising: an exposing step; and a step of developing the exposed photosensitive resin layer to form a pattern in this order.
  • ⁇ 12> The step of bringing the outermost layer on the photosensitive resin layer side of the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 10> into contact with a substrate having a conductive layer, and bonding the photosensitive layer A step of pattern exposing the photosensitive resin layer, a step of developing the exposed photosensitive resin layer to form a pattern, and a step of etching the conductive layer in the region where the pattern is not disposed.
  • a method of manufacturing circuit wiring including the above. ⁇ 13> The method for manufacturing a circuit wiring according to ⁇ 12>, wherein the conductive layer is a layer containing copper.
  • ⁇ 14> The step of bringing the outermost layer on the photosensitive resin layer side of the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 10> into contact with a substrate having a conductive layer, and bonding the photosensitive layer A step of pattern exposing the photosensitive resin layer, a step of developing the exposed photosensitive resin layer to form a pattern, and a step of etching the conductive layer in the region where the pattern is not disposed.
  • a photosensitive transfer material that is excellent in surface shape and excellent in dimple suppression of the resulting pattern.
  • a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method using the photosensitive transfer material can be provided.
  • FIG. 6 is a schematic diagram showing a pattern A.
  • FIG. 6 is a schematic diagram showing a pattern B.
  • symbol may be abbreviate
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • (meth) acryl” represents both and / or acryl and methacryl
  • (meth) acrylate” represents both and / or acrylate and methacrylate.
  • the amount of each component in the composition is the sum of the plurality of corresponding substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition.
  • the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
  • the notation that does not indicate substitution and non-substitution includes those having no substituent and those having a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “exposure” includes not only exposure using light, but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified.
  • an emission ray spectrum of a mercury lamp an actinic ray (active energy ray) such as a far ultraviolet ray, an extreme ultraviolet ray (EUV light) typified by an excimer laser, an X-ray, and an electron beam is used.
  • actinic ray active energy ray
  • EUV light extreme ultraviolet ray
  • the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
  • “mass%” and “weight%” are synonymous, and “part by mass” and “part by weight” are synonymous.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) unless otherwise specified.
  • the molecular weight was detected by a gel permeation chromatography (GPC) analyzer using a THF (tetrahydrofuran) solvent and a differential refractometer, and converted using polystyrene as a standard substance.
  • GPC gel permeation chromatography
  • the photosensitive transfer material according to the present disclosure includes a temporary support and a photosensitive resin layer, and the photosensitive resin layer includes a polymer A including a structural unit having an acid group protected by an acid-decomposable group. , A photoacid generator, and a polymer F containing a structural unit having a fluorine atom, and the fluorine atom content in the polymer F is 20% by mass or more and 50% by mass with respect to the total mass of the polymer F. %, And the polymer F satisfies either f1 or f2 below.
  • f1 The I / O value of the polymer F is 0.45 or more.
  • f2 The polymer F has an I / O value of less than 0.45, and the polymer F includes a structural unit having an acid group or a basic group.
  • the photosensitive transfer material according to the present disclosure is a positive photosensitive transfer material.
  • a small depression called a dimple may be formed on the obtained pattern side wall.
  • the present inventors have found that it is important to make the surfactant hydrophilic in order to improve the dimples. However, it has also been found that when a hydrophilic surfactant is simply used, the surface state of the resulting coating film is deteriorated.
  • the present inventors have found that by using the photosensitive transfer material having the above-described configuration, the surface shape is excellent and the resulting pattern has excellent dimple suppression. Although the detailed expression mechanism of the above effect is unknown, the present inventors presume as follows. In the photosensitive transfer material, the upper and lower sides of the photosensitive resin layer are inverted before and after transfer to the substrate, so that the surfactant present on the surface of the photosensitive resin layer is present at the substrate interface. Conceivable. At this time, it is presumed that the surfactant is diffused into the film in the photosensitive resin layer after transfer whose surface has changed.
  • the polymer F when the polymer F satisfies either f1 or f2, in the photosensitive resin layer, the polymer F coordinates to the photoacid generator and the acid generated by exposure.
  • the photoacid generator and the generated acid are sufficiently dispersed, the formation of local hydrophilic parts due to the generated acid is suppressed, and the formation of portions with different alkali dissolution rates is suppressed, so that the generation of dimples is suppressed. It is estimated that it was made.
  • the content of fluorine atoms in the polymer F is 20% by mass or more and 50% by mass or less with respect to the total mass of the polymer F, the surface state of the obtained coating film is improved. Estimated.
  • FIG. 1 schematically illustrates an example of a layer configuration of a photosensitive transfer material according to the present disclosure.
  • the photosensitive resin layer 12 includes a polymer A containing a structural unit having an acid group protected with an acid-decomposable group, a photoacid generator, and a heavy polymer containing a structural unit having a fluorine atom.
  • the content of fluorine atoms in the polymer F is 20% by mass to 50% by mass with respect to the total mass of the polymer F, and the polymer F is either f1 or f2.
  • the temporary support is a support that supports the photosensitive resin layer and can be peeled off.
  • the temporary support used in the present disclosure preferably has light transmittance from the viewpoint that the photosensitive resin layer can be exposed through the temporary support when the photosensitive resin layer is subjected to pattern exposure.
  • having light transmittance means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of light used for pattern exposure is exposure. From the viewpoint of improving sensitivity, 60% or more is preferable, and 70% or more is more preferable.
  • Examples of the method for measuring the transmittance include a method of measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
  • Examples of the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is particularly preferable from the viewpoints of strength and flexibility.
  • Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a biaxially stretched polyethylene terephthalate film is particularly preferable.
  • the thickness of the temporary support is not particularly limited, but is preferably in the range of 5 ⁇ m to 200 ⁇ m, and more preferably in the range of 10 ⁇ m to 150 ⁇ m in terms of ease of handling and versatility.
  • the thickness of the temporary support is selected according to the material from the viewpoints of strength as a support, flexibility required for bonding to a wiring forming substrate, light transmittance required in the first exposure process, and the like. That's fine.
  • the photosensitive transfer material according to the present disclosure includes at least a temporary support and a photosensitive resin layer, and the photosensitive resin layer includes a structural unit having an acid group protected with an acid-decomposable group.
  • A a photoacid generator, and a polymer F containing a structural unit having a fluorine atom, and the fluorine atom content in the polymer F is 20% by mass or more to 50% by mass with respect to the total mass of the polymer F.
  • the polymer F satisfies either f1 or f2 below.
  • f1 The I / O value of the polymer F is 0.45 or more.
  • the polymer F has an I / O value of less than 0.45, and the polymer F includes a structural unit having an acid group or a basic group.
  • the photosensitive resin layer is preferably a chemically amplified positive photosensitive resin layer.
  • Photo acid generators such as onium salts and oxime sulfonate compounds described below are used to deprotect protected acid groups in binders in which the acid produced in response to actinic rays has acid groups protected by acid degradation.
  • the acid produced by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as the power of 10 High sensitivity is obtained as a result of so-called chemical amplification.
  • NQD quinonediazide compound
  • the photosensitive resin layer includes a polymer F containing a structural unit having a fluorine atom, and the fluorine atom content in the polymer F is 20% by mass or more and 50% by mass with respect to the total mass of the polymer F.
  • the polymer F satisfies either f1 or f2 below.
  • f1 The I / O value of the polymer F is 0.45 or more.
  • f2 The polymer F has an I / O value of less than 0.45, and the polymer F includes a structural unit having an acid group or a basic group.
  • the polymer F is preferably an addition polymerization type resin, and more preferably a polymer having a structural unit derived from (meth) acrylic acid or an ester thereof.
  • the fluorine atom content in the polymer F is 20% by mass or more and 50% by mass or less with respect to the total mass of the polymer F.
  • the fluorine atom content in the polymer F is preferably 20% by mass or more and 45% by mass or less, and preferably 20% by mass or more and 40% by mass or less from the viewpoint of suppressing dimple generation and a planar shape in the obtained pattern. The following is more preferable.
  • the fluorine atom content in the polymer F in the present disclosure is the mass-based fluorine atom content with respect to the entire polymer F.
  • the chemical structure analysis or elemental analysis of the polymer F is performed (in the polymer F It can be calculated from (total mass of fluorine atoms) / (total mass of polymer F).
  • the I / O value of the polymer F is not particularly limited. However, when the I / O value of the polymer F is less than 0.45, the polymer F has an acid group or a basic group described later. Including structural units.
  • the I / O value in the present disclosure is an I / O value obtained by dividing the inorganic value I based on the organic conceptual diagram by the organic value O. Regarding the above I / O values, organic conceptual diagram (Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Nos. 1-16 (1954); Chemistry, Volume 11, Vol. No.
  • the concept of the I / O value is that the properties of a compound are divided into an organic group that represents covalent bonding and an inorganic group that represents ionic bonding, and all organic compounds are orthogonal coordinates named organic axes and inorganic axes. Each of the above points is shown.
  • the I / O value of the polymer F is preferably 0.20 or more, more preferably 0.30 or more, and more preferably 0.30 or more from the viewpoint of suppressing the occurrence of dimples in the resulting pattern. More preferably, it is 50 or less.
  • the polymer F preferably includes a structural unit having an acid group or a basic group, and more preferably satisfies the above f2, from the viewpoint of suppressing the generation of dimples in the pattern to be obtained and a planar shape.
  • the ratio of the I / O value I A of the I / O value I F and the polymer A of the polymer F is in view of suppressing generation and surface dimple in patterns obtained Therefore, it is preferably 0.4 to 3, more preferably 0.5 to 2.5, still more preferably 0.5 to 1.2, and 0.5 or more and less than 1.0. It is particularly preferred. Further, when the polymer F contains a structural unit having an acid group or a basic group, the polymer is more than the I / O value of the polymer F from the viewpoint of suppressing the occurrence of dimples in the obtained pattern and the surface shape. It is preferable that A has a large I / O value.
  • the glass transition temperature (Tg) of the polymer F is preferably 90 ° C. or less, and more preferably 50 ° C. or less, from the viewpoints of pattern formability, transferability, and surface shape of the resulting pattern.
  • the temperature is more preferably ⁇ 30 ° C. or more and 50 ° C. or less, and particularly preferably ⁇ 10 ° C. or more and 20 ° C. or less.
  • the glass transition temperature of the polymer F is lower than the glass transition temperature of the polymer A from a viewpoint of pattern formability, transferability, and the surface shape of the pattern to be obtained. More preferably, it is 10 to 100 ° C. lower than the temperature, more preferably 40 to 90 ° C. lower than the glass transition temperature of the polymer A, and 60 to 80 ° C. lower than the glass transition temperature of the polymer A. Is particularly preferred.
  • the glass transition temperature of the polymer in the present disclosure can be measured using differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • a specific measuring method is performed in accordance with the method described in JIS K 7121 (1987).
  • Tig extrapolated glass transition start temperature
  • the method for measuring the glass transition temperature will be described more specifically.
  • the heating rate is about 30 ° C./minute at a heating rate of 20 ° C./min. Heat to a higher temperature and draw a DTA or DSC curve.
  • the extrapolated glass transition start temperature (Tig) that is, the glass transition temperature Tg in the present specification, is a straight line obtained by extending the low-temperature base line in the DTA curve or DSC curve to the high-temperature side, and the stepwise change portion of the glass transition. Calculated as the temperature of the intersection with the tangent drawn at the point where the slope of the curve is maximum.
  • the FOX formula is used as a guideline. It is possible to control the Tg of the target polymer.
  • Tg of the homopolymer of the first structural unit contained in the polymer is Tg1
  • the mass fraction in the copolymer of the first structural unit is W1
  • the Tg of the homopolymer of the second structural unit Is Tg2 and the mass fraction in the copolymer of the second structural unit is W2
  • the Tg0 (K) of the copolymer containing the first structural unit and the second structural unit is It is possible to estimate according to the equation.
  • FOX formula: 1 / Tg0 (W1 / Tg1) + (W2 / Tg2)
  • a copolymer having a desired Tg can be obtained by adjusting the type and mass fraction of each structural unit contained in the copolymer using the FOX formula described above. It is also possible to adjust the Tg of the polymer by adjusting the weight average molecular weight of the polymer.
  • the weight average molecular weight (Mw) of the polymer F is preferably 2,000 or more, more preferably 2,000 to 100,000, and still more preferably 2,000 to 20,000.
  • the weight average molecular weight and number average molecular weight of the polymer F and the polymer A can be measured by GPC (gel permeation chromatography), and various commercially available apparatuses can be used as the measuring apparatus.
  • GPC gel permeation chromatography
  • various commercially available apparatuses can be used as the measuring apparatus.
  • the contents of the device and the measurement technique are known to those skilled in the art.
  • HLC registered trademark
  • -8220GPC manufactured by Tosoh Corporation
  • TSKgel registered trademark
  • Super HZM-M 4 .6 mm ID ⁇ 15 cm, manufactured by Tosoh Corporation
  • Super HZ4000 4 mm ID ⁇ 15 cm, manufactured by Tosoh Corporation
  • Super HZ3000 4 mm ID ⁇ 15 cm, manufactured by Tosoh Corporation
  • Super HZ2000 4 mm ID
  • THF tetrahydrofuran
  • the measurement conditions are 0.2 mass%, the flow rate is 0.35 ml / min, the sample injection amount is 10 ⁇ l, the measurement temperature is 40 ° C., and a differential refractive index (RI) detector is used. be able to.
  • the calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “ It can be produced using at least two of any of the seven samples of “A-2500” and “A-1000”.
  • the ratio (Mw / Mn, degree of dispersion) of the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer F is preferably 1.0 to 5.0, more preferably 1.05 to 3.5. .
  • the polymer F includes a structural unit having a fluorine atom.
  • the number of fluorine atoms in the structural unit having a fluorine atom may be any number that satisfies the content of the fluorine atom. It is more preferably 30 or less, and further preferably 7 or more and 20 or less.
  • the structural unit having a fluorine atom preferably has a fluorine atom as a perfluoroalkyl group or a perfluoroaryl group, more preferably as a perfluoroalkyl group, from the viewpoint of planarity at the time of coating.
  • the structural unit having a fluorine atom preferably has a perfluoroalkyl group or a perfluoroaryl group, and more preferably has a perfluoroalkyl group, from the viewpoint of planarity at the time of coating.
  • the number of carbon atoms of the perfluoroalkyl group is preferably 4 or more and 30 or less, more preferably 6 or more and 24 or less, and particularly preferably 9 or more and 15 or less, from the viewpoint of the surface state during coating. .
  • the structural unit having a fluorine atom is preferably a structural unit represented by the following formula F-1 from the viewpoint of planarity during coating.
  • R f1 represents a hydrogen atom or a methyl group
  • X f1 represents a single bond, —COO—, —OCO—, or an arylene group
  • L f1 represents a single bond, an alkylene group, Alternatively, it represents a group in which two or more groups selected from the group consisting of an alkylene group, —COO—, —OCO—, and an arylene group are bonded
  • Rf represents a perfluoroalkyl group.
  • X f1 in formula F-1 is preferably a single bond or —COO—, more preferably —COO—, from the viewpoints of availability and synthesis suitability.
  • L f1 in Formula F-1 is an alkylene group or a group obtained by bonding two or more groups selected from the group consisting of —COO—, —OCO— and an arylene group from the viewpoints of availability and synthesis suitability.
  • An alkylene group or a group formed by bonding two or more groups selected from the group consisting of —COO— and —OCO— is more preferable, and an alkylene group is particularly preferable.
  • the alkylene group may be linear, branched, or have a ring structure.
  • the alkylene group is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably a methylene group or an ethylene group.
  • Rf in Formula F-1 is preferably a perfluoroalkyl group having 4 to 30 carbon atoms, more preferably a perfluoroalkyl group having 4 to 24 carbon atoms, from the viewpoint of the surface state during coating.
  • a perfluoroalkyl group having 9 to 15 carbon atoms is particularly preferable.
  • the perfluoroalkyl group may be linear, branched, or have a ring structure, but it is possible to suppress dimple generation in the pattern obtained and to obtain a planar view at the time of coating. Therefore, a linear or branched perfluoroalkyl group is preferable, and a linear perfluoroalkyl group is more preferable.
  • the polymer F may have the structural unit which has a fluorine atom individually by 1 type, or may have 2 or more types.
  • the structural unit having a fluorine atom is preferably a structural unit different from the structural unit having an acid group or basic group and the structural unit having a hydrophilic group, which will be described later. Moreover, it is preferable that the structural unit which has an acid group or a basic group, and the structural unit which has a hydrophilic group do not have a fluorine atom.
  • the polymer F preferably contains 20% by mass or more and 99% by mass or less, and 30% by mass or more and 99% by mass or less of a structural unit having a fluorine atom with respect to the total mass of the polymer F, from the viewpoint of planarity at the time of coating. More preferably, it is more preferably 30% by mass or more and 95% by mass or less, and particularly preferably 35% by mass or more and 70% by mass or less.
  • the content (content ratio: mass ratio) of the structural unit having a fluorine atom in the polymer F can be confirmed by the intensity ratio of the peak intensity calculated by 13 C-NMR measurement or 19 F-NMR measurement by a conventional method. it can.
  • the polymer F includes a structural unit having an acid group or a basic group. Moreover, it is preferable that the said polymer F contains the structural unit which has an acid group or a basic group from a viewpoint of generation
  • the acid group in this specification means a proton dissociable group having a pKa of 11 or less.
  • the acid group is incorporated into the polymer as a structural unit having an acid group using, for example, a monomer capable of forming an acid group.
  • the pKa of the acid group is preferably 10 or less, and more preferably 6 or less.
  • the pKa of the acid group is preferably ⁇ 5 or more.
  • the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonylimide group.
  • At least one acid group selected from the group consisting of a carboxy group and a phenolic hydroxyl group is preferable.
  • the introduction of the structural unit having an acid group into the polymer can be carried out by copolymerizing a monomer having an acid group.
  • the structural unit having an acid group is more preferably a structural unit derived from styrene or a structural unit obtained by substituting an acid group for a structural unit derived from a vinyl compound, or a structural unit derived from (meth) acrylic acid. preferable.
  • the structural unit having an acid group is preferably a structural unit having a carboxy group or a structural unit having a phenolic hydroxyl group, from the viewpoint of pattern formation and suppression of the occurrence of dimples in the resulting pattern, and has a carboxy group.
  • a structural unit is more preferable.
  • the monomer having an acid group that can form a structural unit having an acid group is not limited to the examples described above.
  • the structural unit having an acid group contained in the polymer F may be only one type or two or more types.
  • the polymer F contains 0.1% by mass to 20% by mass of a structural unit having an acid group with respect to the total mass of the polymer F, from the viewpoints of pattern formability and suppression of occurrence of dimples in the resulting pattern.
  • the content is preferably 0.5% by mass to 15% by mass, more preferably 1% by mass to 10% by mass.
  • the content (content ratio: mass ratio) of the structural unit having an acid group in the polymer F can be confirmed by the intensity ratio of the peak intensity calculated by 13 C-NMR measurement by a conventional method.
  • the basic group is preferably a group having a nitrogen atom from the viewpoint of pattern formation and suppression of dimple formation in the resulting pattern, and is preferably an aliphatic amino group, an aromatic amino group, or a nitrogen-containing complex. It is more preferably an aromatic ring group, further preferably an aliphatic amino group or a nitrogen-containing heteroaromatic ring group, and particularly preferably an aliphatic amino group.
  • the aliphatic amino group may be any of a primary amino group, a secondary amino group, or a tertiary amino group, but from the viewpoint of suppressing the occurrence of dimples in the pattern obtained and a planar shape, It is preferably a secondary amino group or a tertiary amino group, more preferably a tertiary amino group.
  • the tertiary amino group is preferably a dialkylamino group or an N-alkylmorpholino group.
  • the structural unit having a basic group is preferably a structural unit derived from a (meth) acrylate compound.
  • the structural unit having a basic group contained in the polymer F may be only one type or two or more types. From the viewpoints of pattern formability and suppression of dimple formation in the resulting pattern, the polymer F contains 0.1% by mass to 50% by mass of a structural unit having a basic group with respect to the total mass of the polymer F. It is preferably contained, more preferably 1% by mass to 40% by mass, and even more preferably 5% by mass to 30% by mass.
  • the content (content ratio: mass ratio) of the structural unit having a basic group in the polymer F can be confirmed by the intensity ratio of peak intensity calculated by 13 C-NMR measurement by a conventional method.
  • the structural unit having an acid group or basic group is preferably a structural unit represented by the following formula F-2 from the viewpoint of suppressing the occurrence of dimples in the resulting pattern.
  • R f2 represents a hydrogen atom or a methyl group
  • X f2 represents a single bond, —COO—, —OCO—, or an arylene group
  • L f2 represents a single bond, an alkylene group, Alternatively, it represents a group in which two or more groups selected from the group consisting of an alkylene group, —COO—, —OCO— and an arylene group are bonded
  • R p represents an acid group or a basic group.
  • X f2 in formula F-2 is preferably a single bond or —COO— from the viewpoint of availability and synthesis suitability.
  • L f2 in Formula F-2 is a single bond, an alkylene group, or two or more groups selected from the group consisting of an alkylene group, —COO—, and —OCO— bonded from the viewpoint of availability and synthesis suitability. It is preferably a group, more preferably a single bond or an alkylene group.
  • the alkylene group may be linear, branched, or have a ring structure.
  • the alkylene group is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably an ethylene group or a propylene group.
  • Rp in Formula F-2 is preferably a carboxy group or a group having a nitrogen atom from the viewpoint of suppressing the occurrence of dimples in the resulting pattern, and is a group having a carboxy group or a tertiary amino group. More preferred is a carboxy group, a dialkylamino group or an N-alkylmorpholino group.
  • the structural unit which has the said acid group or basic group may further have the hydrophilic group mentioned later other than an acid group and a basic group.
  • the structural unit having an acid group or a basic group is a structural unit different from the structural unit having a hydrophilic group described later.
  • the polymer F preferably contains a structural unit having a hydrophilic group, and more preferably contains a structural unit having a hydrophilic group in the side chain, from the viewpoint of suppressing the occurrence of dimples in the resulting pattern.
  • main chain represents a relatively long bond chain in the molecule of the polymer compound constituting the resin
  • side chain represents a carbon chain branched from the main chain.
  • Hydrophilic groups include hydroxy group, ether bond, thioether bond, carbonyl group, amide structure, lactone structure, ester bond, thioester bond, urea bond, thiourea bond from the viewpoint of suppressing dimple generation in the resulting pattern and planarity.
  • At least one structure selected from the group consisting of a urethane bond and a cyano group is preferred, a hydroxy group, an ether bond, a thioether bond, a carbonyl group, an amide structure, a lactone structure, a thioester bond, a urea bond, a thiourea bond, and a urethane More preferable is at least one structure selected from the group consisting of a bond and a cyano group, and at least selected from the group consisting of a hydroxy group, an ether bond, an amide structure, a lactone structure, a urea bond, a urethane bond, and a cyano group.
  • the polymer F has a hydroxy group, an ether bond, a thioether bond, a carbonyl group, an amide structure, a lactone structure, an ester bond, and a thioester bond from the viewpoint of suppressing the occurrence of dimples in the resulting pattern and the surface state during coating.
  • the cyclic ether group is preferably a group having a 4-membered to 6-membered cyclic ether ring, more preferably a group having a 5-membered or 6-membered cyclic ether ring.
  • a group having a cyclic ether ring is particularly preferred.
  • the cyclic ether group is preferably a tetrahydrofuranyl group or a tetrahydropyranyl group, and more preferably a tetrahydrofuranyl group.
  • the carbonyl group and the ether bond mean a carbonyl group and an ether bond that do not form an ester bond.
  • the structural unit having hydrophilicity is preferably a structural unit represented by the following formula F-3, from the viewpoint of suppressing the generation of dimples in the pattern obtained and the surface state during coating.
  • R f3 represents a hydrogen atom or a methyl group
  • X f3 represents a single bond, —COO—, —OCO—, —CONR a —, or an arylene group
  • L f3 represents a single bond
  • R aq represents a hydrophilic group.
  • R a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • X f3 in formula F-3 is preferably —COO— or —CONR a —, more preferably —COO—, from the viewpoint of availability and synthesis suitability.
  • L f3 in Formula F-3 is an alkylene group or a group selected from the group consisting of —COO—, —OCO—, —O—, and an arylene group from the viewpoints of availability, synthesis suitability, and planarity.
  • An alkylene group or a group selected from the group consisting of —COO— and —OCO— is more preferable, and an alkylene group is particularly preferable.
  • the alkylene group may be linear, branched, or have a ring structure.
  • the alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably a methylene group or an ethylene group.
  • R aq in Formula F-3 is a hydroxy group, an ether bond, a thioether bond, a carbonyl group, an amide structure, a lactone structure, an ester bond, a thioester bond, or a urea bond, from the viewpoint of suppressing the dimple generation in the obtained pattern.
  • At least one structure selected from the group consisting of a thiourea bond, a urethane bond, and a cyano group is preferable, and is preferably a hydroxy group, a cyclic ether group, a polyalkyleneoxy group, an alkyleneoxy group, or a cyano group, More preferably, it is a hydroxy group, an alkyleneoxy group or a cyclic ether group.
  • the polymer F may have the structural unit which has a hydrophilic group individually by 1 type, or may have 2 or more types.
  • the polymer F includes a structural unit having a hydrophilic group
  • the polymer F is hydrophilic from the viewpoints of pattern formability, transferability, generation of dimples in the resulting pattern, and surface conditions during coating.
  • the structural unit having a functional group is preferably contained in an amount exceeding 0% by mass and 70% by mass or less, more preferably 5% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 65% by mass with respect to the total mass of the polymer F. More preferably, it is contained in an amount of 20% by mass or less, and particularly preferably 20% by mass or more and 60% by mass or less.
  • the content (content ratio: mass ratio) of the structural unit having a hydrophilic group in the polymer F can be confirmed by an intensity ratio of peak intensities calculated by a conventional method from 13 C-NMR measurement.
  • the polymer F preferably includes a structural unit having an acid group protected with an acid-decomposable group, from the viewpoint of suppressing the occurrence of dimples in the pattern to be obtained and the surface state during coating.
  • a structural unit having an acid group protected with an acid-decomposable group those similar to the structural unit having an acid group protected with an acid-decomposable group in polymer A described later can be applied.
  • 70 mass% or less is preferable with respect to the total mass of the polymer F, and, as for content of the structural unit which has the acid group protected by the acid-decomposable group in the said polymer F, 50 mass% or less is more preferable, 50 A mass% or less is more preferable.
  • the lower limit may be 0% by mass, but is preferably 1% by mass or more, and more preferably 5% by mass or more. Within the above range, the resolution and adhesion are further improved.
  • the content (content ratio: mass ratio) of other structural units in the polymer F can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from 13 C-NMR measurement.
  • the polymer F has the above-described constitutional unit having a fluorine atom, a constitutional unit having an acid group or a basic group, a constitutional unit having a hydrophilic group, and an acid group protected with an acid-decomposable group.
  • Other structural units other than the units may be included within a range not impairing the effects of the photosensitive transfer material according to the present disclosure.
  • styrenes (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid
  • examples include diesters, bicyclounsaturated compounds, unsaturated aromatic compounds, conjugated diene compounds, and other unsaturated compounds.
  • Various characteristics of the polymer can be adjusted by adjusting at least one of the type and content using other structural units. In particular, the Tg of the polymer can be easily adjusted by appropriately using other structural units.
  • (meth) acrylic acid alkyl ester is preferable from the viewpoint of suppressing the occurrence of dimples in the resulting pattern.
  • (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion.
  • Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • the said polymer F may contain only 1 type of other structural units, and may contain 2 or more types. 70 mass% or less is preferable with respect to the total mass of the polymer F, as for content of the other structural unit in the said polymer F, 60 mass% or less is more preferable, and 50 mass% or less is still more preferable.
  • the lower limit may be 0% by mass, but is preferably 1% by mass or more, and more preferably 5% by mass or more. Within the above range, the resolution and adhesion are further improved.
  • the content (content ratio: mass ratio) of other structural units in the polymer F can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from 13 C-NMR measurement.
  • the other structural unit in the polymer F is preferably a structural unit having a carboxylic acid ester structure, and more preferably a structural unit derived from an alkyl (meth) acrylate. preferable. Further, from the viewpoint of transferability and pattern formability, the other structural unit in the polymer F is preferably a structural unit represented by the following formula F-4.
  • R f4 represents a hydrogen atom or a methyl group
  • X f4 represents a single bond, —COO—, —OCO—, or an arylene group
  • L f4 represents a single bond, an alkylene group, Or a group in which two or more groups selected from the group consisting of an alkylene group, —COO—, —OCO—, and an arylene group are bonded
  • R al represents a linear, branched, or cyclic alkyl group, or an aryl group Represents.
  • X f4 in formula F-4 is preferably a single bond or —COO—, more preferably —COO—, from the viewpoints of availability and synthesis suitability.
  • L f4 in Formula F-4 is preferably a single bond from the viewpoints of availability and synthesis suitability.
  • R al in formula F-4 is preferably a linear, branched or cyclic alkyl group, more preferably a linear or cyclic alkyl group, from the viewpoint of transferability and pattern formation.
  • the carbon number of R al in Formula F-4 is preferably 1 to 30, more preferably 8 to 20, and more preferably 10 to 20 from the viewpoints of transferability and pattern formability. Particularly preferred.
  • R al in Formula F-4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl, cyclohexyl group, 2-ethylhexyl group, n from the viewpoint of transferability and pattern formation.
  • -Octyl group, n-decyl group, n-dodecyl group, dicyclopentanyl group, and benzyl group are preferred, and cyclohexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group, n-dodecyl group More preferred are a group and a dicyclopentanyl group, and particularly preferred are an n-dodecyl group and a dicyclopentanyl group.
  • the said polymer F may contain only 1 type of other structural units, and may contain 2 or more types.
  • the structural unit represented by the formula F-4 is all of the polymer F from the viewpoint of transferability and pattern formation. 1% to 70% by mass, preferably 10% to 60% by mass, more preferably 20% to 50% by mass, and more preferably 25% to 50% by mass with respect to the mass. It is particularly preferred.
  • the polymer F only needs to contain a structural unit having a fluorine atom, but from the viewpoints of transferability, pattern formation, and dimple generation suppression and planarity in the resulting pattern, the structural unit having a fluorine atom. It is preferable to include a structural unit having a hydrophilic group, and it is more preferable to include a structural unit having a fluorine atom, a structural unit having a hydrophilic group, and a structural unit having an acid group or a basic group.
  • the polymer F As the form contained in the polymer F, from the viewpoints of transferability, pattern formation, dimple generation suppression and planarity in the resulting pattern, the structural unit represented by the formula F-1, and A form including the structural unit represented by F-3, the structural unit represented by Formula F-1, the structural unit represented by F-3, and Formula F-2 or Formula F- The form containing the structural unit represented by 4 is mentioned. Further, the polymer F is preferably a polymer represented by the following formula F-5 from the viewpoints of transferability, pattern formation, and dimple generation suppression and planarity in the resulting pattern.
  • R f1 to R f4 each independently represents a hydrogen atom or a methyl group
  • X f1 to X f4 each independently represents a single bond, —COO—, —OCO—, or an arylene group
  • L f1 to L f4 each independently represents a single bond, an alkylene group, or a group in which two or more groups selected from the group consisting of an alkylene group, —COO—, —OCO—, and an arylene group are bonded.
  • Rf represents a perfluoroalkyl group
  • R p represents an acid group or a basic group
  • R aq represents a hydrophilic group
  • R al represents a linear, branched or cyclic alkyl group
  • aryl R1 to r4 represent the mass ratio of each structural unit, the sum of r1 + r2 + r3 + r4 is 100, r1 represents 30 to 99, r2 to r4 each independently represents 0 to 70, r2 to r4 out of r4 One even without is greater than or equal to 1.
  • R f1 to R f4 , X f1 to X f4 , L f1 to L f4 , Rf, R p , R aq , and R al in the above formula F-5 are R in the above formulas F-1 to F-4.
  • f1 to R f4 , X f1 to X f4 , L f1 to L f4 , Rf, R p , R aq , and R al are synonymous with each other, and preferred embodiments are also the same.
  • r1 is preferably from 30 to 95, more preferably from 35 to 70, from the viewpoint of planarity.
  • r2 is preferably from 0 to 50, more preferably from 0 to 40, and even more preferably from 0 to 30 from the viewpoints of pattern formability and suppression of dimple generation in the resulting pattern.
  • r2 is 1 to 50 from the viewpoints of pattern formation, suppression of dimple generation in the resulting pattern, and planar shape. It is preferably 5 to 40, more preferably 10 to 30.
  • r3 is preferably from 0 to 70, more preferably from 0 to 60, from the viewpoint of suppressing the occurrence of dimples in the resulting pattern.
  • r3 is 5 to 70 from the viewpoints of transferability, pattern formation, and dimple generation suppression and planarity in the resulting pattern. It is preferably 10 to 65, more preferably 20 to 60.
  • r4 is preferably from 0 to 60, more preferably from 0 to 50, from the viewpoints of transferability and pattern formability.
  • r4 is 1 to 70 from the viewpoints of pattern formability, suppression of dimple generation in the obtained pattern, and planarity. It is preferably 10 to 60, more preferably 20 to 50, and particularly preferably 25 to 50.
  • r1 When r2 is 0, it is preferable that r1 is 30 to 95, r3 is 5 to 70, and r4 is 0 to 65 from the viewpoint of planarity. Further, when r2 is 1 to 70, it is preferable that r1 is 30 to 99, r3 is 0 to 69, and r4 is 0 to 69 from the viewpoint of planarity.
  • the production method (synthesis method) of the polymer F is not particularly limited.
  • a polymerizable monomer for forming a structural unit having a fluorine atom, and, if necessary, an acid group or a basic group for example, Polymerization using a polymerization initiator in an organic solvent containing a polymerizable monomer for forming a structural unit having a polymerizable monomer and a polymerizable monomer for forming a structural unit having a hydrophilic group Can be synthesized. It can also be synthesized from other polymers by so-called polymer reaction.
  • the said photosensitive resin layer may contain the said polymer F individually by 1 type, or may contain 2 or more types.
  • the photosensitive resin layer contains the polymer F in a proportion of 0.005% by mass to 5% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of suppression of dimple generation and a planar shape in the obtained pattern. Preferably, it is contained in a proportion of 0.01% by mass to 1% by mass, particularly preferably in a proportion of 0.05% by mass to 0.5% by mass.
  • the mass ratio (M A / M F ) of the polymer A content M A and the polymer F content M F described later in the photosensitive resin layer is determined by the suppression of the occurrence of dimples in the obtained pattern and From the viewpoint of planarity, it is preferably 10 to 10,000, more preferably 50 to 5,000, and particularly preferably 100 to 3,000.
  • the photosensitive resin layer includes a polymer A including a structural unit having an acid group that is protected by acid decomposition (also referred to as “structural unit A”).
  • the content of fluorine atoms in the polymer A is preferably 10% by mass or less, more preferably 5% by mass or less, particularly not containing fluorine atoms, with respect to the total mass of the polymer A. preferable.
  • the polymer A does not contain the structural unit which has a fluorine atom.
  • the photosensitive resin layer may contain another polymer in addition to the polymer F and the polymer A.
  • the structural unit A having an acid-decomposable protected acid group in the polymer A undergoes a deprotection reaction to be an acid group by the action of a catalytic amount of an acidic substance generated by exposure. This acid group enables a curing reaction.
  • the preferable aspect of the polymer A is demonstrated.
  • the polymer A is preferably an addition polymerization type resin, and more preferably a polymer having a structural unit derived from (meth) acrylic acid or an ester thereof.
  • the photosensitive resin layer is composed of a polymer having a structural unit represented by the following formula A as the structural unit A as the polymer A from the viewpoint of suppressing deformation of the pattern shape, solubility in a developer, and transferability.
  • the polymer A preferably includes a polymer A having the structural unit represented by the following formula A as the structural unit A and having a glass transition temperature of 90 ° C. or lower.
  • As the structural unit A it is more preferable to include a polymer A having a structural unit represented by the following formula A and a structural unit having an acid group described later and having a glass transition temperature of 90 ° C. or lower.
  • the polymer A contained in the photosensitive resin layer may be one type or two or more types.
  • the acid value of the polymer A is preferably 1.5 mmol / g or less, more preferably 1.0 mmol / g or less, and 0.5 mmol / g. It is particularly preferred that it is g or less.
  • the lower limit of the acid value is 0 mmol / g.
  • the acid value means a value measured according to the method described in JIS K0070 (1992).
  • the glass transition temperature (Tg) of the polymer A in the present disclosure is preferably 90 ° C. or lower.
  • Tg is 90 ° C. or lower
  • the Tg of the polymer A is more preferably 60 ° C. or less, and further preferably 40 ° C. or less.
  • the lower limit of Tg of the polymer A is not particularly limited, but is preferably ⁇ 20 ° C. or higher, more preferably ⁇ 10 ° C. or higher.
  • the Tg of the polymer A is ⁇ 20 ° C. or higher, good pattern formability is maintained. For example, when a cover film is used, the adhesion of the cover film is poor, or peeling when the cover film is peeled off Defects are suppressed.
  • the I / O value of the polymer A is preferably 1.00 or less, more preferably 0.80 or less, and 0.65 or less from the viewpoint of storage stability of the photosensitive transfer material. It is particularly preferred. Further, the lower limit value of the I / O value of the polymer A is preferably 0.30 or more, more preferably 0.40 or more, and 0.50 or more from the viewpoint of formability. Is particularly preferred.
  • the weight average molecular weight (Mw) of the polymer A is preferably 60,000 or less.
  • the weight average molecular weight of the polymer A is more preferably 2,000 to 60,000, and further preferably 3,000 to 50,000.
  • the ratio (Mw / Mn, degree of dispersion) of the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer A is preferably 1.0 to 5.0, more preferably 1.05 to 3.5. .
  • the polymer A includes at least a structural unit having an acid group protected with an acid-decomposable group.
  • the photosensitive resin layer can be an extremely sensitive chemically amplified positive photosensitive resin layer.
  • the “acid group protected with an acid-decomposable group” in the present disclosure may be any known acid group and acid-decomposable group, and is not particularly limited. Specific examples of the acid group preferably include a carboxy group and a phenolic hydroxyl group.
  • the acid group protected with an acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an ester group, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester protected with a group represented by the formula A).
  • An acetal functional group such as a group) or a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).
  • the acid-decomposable group is preferably a group having a structure protected in the form of an acetal from the viewpoint of sensitivity and resolution.
  • the structural unit having an acid group protected with an acid-decomposable group is preferably a structural unit represented by the following formula A from the viewpoint of sensitivity and resolution.
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group or Represents an aryl group, and R 31 or R 32 and R 33 may combine to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or a divalent linking group. Represents.
  • R 31 or R 32 when R 31 or R 32 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R 31 or R 32 is an aryl group, a phenyl group is preferable. R 31 and R 32 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 33 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Further, the alkyl group and aryl group in R 31 to R 33 may have a substituent.
  • R 31 or R 32 and R 33 may be linked to form a cyclic ether, and R 31 or R 32 and R 33 are preferably linked to form a cyclic ether.
  • the number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
  • X 0 represents a single bond or an arylene group, and a single bond is preferable.
  • the arylene group may have a substituent.
  • the structural unit represented by the formula A is a structural unit having a carboxy group protected with an acid-decomposable group. When the polymer A contains the structural unit represented by the formula A, the sensitivity at the time of pattern formation is excellent and the resolution is superior.
  • R 34 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the Tg of the polymer A can be further lowered. More specifically, with respect to the total amount of the structural unit represented by the formula A contained in the polymer A, the structural unit in which R 34 in the formula A is a hydrogen atom is preferably 20% by mass or more.
  • the content (content ratio: mass ratio) of the structural unit in which R 34 in Formula A is a hydrogen atom in the structural unit having an acid group protected with an acid-decomposable group is 13 C-nuclear magnetic resonance. It can be confirmed by the intensity ratio of the peak intensity calculated from the spectrum (NMR) measurement by a conventional method.
  • the structural unit represented by the following formula A2 is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.
  • R 34 represents a hydrogen atom or a methyl group
  • R 35 to R 41 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 34 is preferably a hydrogen atom.
  • R 35 to R 41 are preferably hydrogen atoms.
  • R 34 represents a hydrogen atom or a methyl group.
  • the structural unit having an acid group protected with an acid-decomposable group is preferably a structural unit represented by the following formula A3 from the viewpoint of suppressing deformation of the pattern shape.
  • R B1 and R B2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R B1 and R B2 is an alkyl group or an aryl group, and R B3 is an alkyl group or Represents an aryl group, R B1 or R B2 and R B3 may be linked to form a cyclic ether, R B4 represents a hydrogen atom or a methyl group, and X B represents a single bond or a divalent linking group; R B12 represents a substituent, and n represents an integer of 0 to 4.
  • R B1 or R B2 when R B1 or R B2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R B1 or R B2 is an aryl group, a phenyl group is preferable.
  • R B1 and R B2 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R B3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group and aryl group in R B1 to R B3 may have a substituent.
  • R B1 or R B2 and R B3 may be linked to form a cyclic ether, and R B1 or R B2 and R B3 are preferably linked to form a cyclic ether.
  • the number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
  • X B represents a single bond or a divalent linking group, and represents a single bond or an alkylene group, —C ( ⁇ O) O—, —C ( ⁇ O) NR N —, —O—, or a combination thereof.
  • the alkylene group may be linear, branched or cyclic, and may have a substituent.
  • the alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • X B contains —C ( ⁇ O) O—
  • an embodiment in which the carbon atom contained in —C ( ⁇ O) O— and the carbon atom bonded to R B4 are directly bonded is preferable.
  • R N represents an alkyl group or a hydrogen atom, preferably an alkyl group or a hydrogen atom having 1 to 4 carbon atoms, more preferably a hydrogen atom.
  • R B12 represents a substituent, and is preferably an alkyl group or a halogen atom.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
  • R B4 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of lowering the Tg of the polymer. More specifically, with respect to the total content of the structural unit having an acid group protected by the acid-decomposable group contained in the polymer, the structural unit in which R B4 in formula A3 is a hydrogen atom is 20% by mass or more. It is preferable that In the structural unit having an acid group protected with an acid-decomposable group, the content (content ratio: mass ratio) of the structural unit in which R B4 in formula A3 is a hydrogen atom is 13 C-nuclear magnetic resonance. It can be confirmed by the intensity ratio of the peak intensity calculated from the spectrum (NMR) measurement by a conventional method.
  • the structural unit represented by the following formula A4 is more preferable from the viewpoint of suppressing deformation of the pattern shape.
  • R B4 represents a hydrogen atom or a methyl group
  • R B5 to R B11 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R B12 represents a substituent
  • n is 0 Represents an integer of ⁇ 4.
  • R B4 is preferably a hydrogen atom.
  • R B5 to R B11 are preferably hydrogen atoms.
  • R B12 represents a substituent, and is preferably an alkyl group or a halogen atom.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
  • R B4 represents a hydrogen atom or a methyl group.
  • the structural unit having an acid group protected by the acid-decomposable group contained in the polymer A may be one type or two or more types.
  • the content of the structural unit having an acid group protected by the acid-decomposable group in the polymer A is preferably 10% by mass or more with respect to the total mass of the polymer A, and is preferably 10% by mass to 90%. More preferably, it is more preferably 20% by mass to 70% by mass.
  • the content (content ratio: mass ratio) of the structural unit having an acid group protected by the acid-decomposable group in the polymer A is determined by the intensity ratio of the peak intensity calculated by a conventional method from 13 C-NMR measurement. Can be confirmed.
  • the polymer A is a structural unit other than a structural unit having an acid group protected by an acid-decomposable group (for example, a structural unit having an acid group or a structure having a basic group). It is preferable to further have units and other structural units).
  • the polymer A preferably contains a structural unit having an acid group from the viewpoints of developability and resolution.
  • the structural unit having an acid group is a structural unit having a protecting group, for example, an acid group not protected by an acid-decomposable group, that is, an acid group having no protecting group.
  • the polymer A contains a polymer having a structural unit having an acid group, the sensitivity at the time of pattern formation becomes good, and it becomes easy to dissolve in an alkaline developer in the development process after pattern exposure, thereby shortening the development time. Can be planned.
  • Preferred examples of the structural unit having an acid group include the structural unit having an acid group in the polymer F.
  • the structural unit having an acid group contained in the polymer A may be one type or two or more types.
  • the polymer A preferably contains 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass of a structural unit having an acid group with respect to the total mass of the polymer A. More preferably, the content is 1% by mass to 10% by mass. When it is in the above range, the pattern formability becomes better.
  • the content (content ratio: mass ratio) of the structural unit having an acid group in the polymer A can be confirmed by the intensity ratio of the peak intensity calculated from 13 C-NMR measurement by a conventional method.
  • the polymer A can further include a structural unit having a pKaH group of 3 or more.
  • the polymer A further includes a structural unit having a pKaH group of 3 or more, thereby suppressing excessive diffusion of the acid generated from the photoacid generator, and resulting from the tailing of the resin pattern during development. The decline in sex can be suppressed.
  • the polymer A further includes a structural unit having a pKaH group of 3 or more, so that the resin obtained even when the photosensitive transfer material is developed after a certain amount of time has passed after exposure. Thinning of the line width of the pattern or the like can be suppressed (hereinafter, sometimes referred to as “retention time dependency suppression”).
  • pKaH refers to the pKa of a conjugate acid.
  • group having a pKaH of 3 or more refers to a group having a pKa of a conjugate acid of the group of 3 or more.
  • the pKaH value of “—NH 2 ” is the pKa value of “—NH 3 + ”.
  • the value of “pKaH” is a calculated value obtained by ACD / ChemSketch (ACD / Labs 8.00 Release Product Version 8.08). Specifically, from the chemical structure of the structural unit having a specific functional group, the above-mentioned ACD / ChemSketch is used to calculate the pKaH value of the specific functional group.
  • the group having a pKaH of 3 or more is preferably a group having a pKaH of 4 or more, more preferably a group having a pKaH of 5 or more, and a pKaH of 5 or more from the viewpoint of resolution and retention time-dependent suppression. More preferably, it is a group of 15 or less, and particularly preferably a group having a pKaH of 6 or more and 10 or less.
  • the polymer A preferably includes a structural unit having a pKaH of 4 or more, more preferably includes a structural unit having a pKaH of 5 or more, and a group having a pKaH of 5 or more and 15 or less.
  • a structural unit it is more preferable to include a structural unit, and it is particularly preferable to include a polymer A having at least a structural unit having a pKaH group of 6 to 10.
  • the structural unit having a basic group include those described in paragraph 0140 of JP-A No. 2015-187634 and paragraphs 0068 to 0070 of JP-A No. 2011-039266.
  • the group having pKaH of 3 or more is preferably a group having a nitrogen atom from the viewpoint of resolution and retention time-dependent suppression, and is an aliphatic amino group, aromatic amino group, or nitrogen-containing heteroaromatic ring. It is more preferably a group, more preferably an aliphatic amino group or a nitrogen-containing heteroaromatic group, and particularly preferably an aliphatic amino group.
  • the aliphatic amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group, but from the viewpoint of resolution and retention time-dependent suppression, A primary amino group or a tertiary amino group is preferred.
  • the aromatic amino group is preferably an anilino group, a monoalkylanilino group, or a dialkylanilino group, and more preferably a monoalkylanilino group or a dialkylanilino group.
  • the nitrogen-containing heteroaromatic ring in the nitrogen-containing heteroaromatic 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. preferable.
  • the nitrogen-containing heteroaromatic group may further 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.
  • the group having a pKaH of 3 or more is particularly preferably a group having an alkylamine structure from the viewpoint of resolution and retention time-dependent suppression.
  • alkylamine structure include dialkylamines and trialkylamines. Specifically, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, 1,2,2,6,6- Examples thereof include a pentaalkyl-4-piperidyl group and a 2,2,6,6-tetraalkyl-4-piperidyl group.
  • Preferred examples of the monomer that forms the structural unit having the alkylamine structure include the following.
  • the structural unit having a pKaH group of 3 or more is preferably a structural unit represented by the following formula I or formula II from the viewpoint of resolution and retention time-dependent inhibition properties, and represented by the following formula I: More preferably, it is a structural unit.
  • R 1 represents a hydrogen atom or a methyl group
  • Z represents a single bond, a methylene group, an arylene group, —O—, —C ( ⁇ O) —NH—, or —C ( ⁇ O) —.
  • R 2 may have a single bond or at least one group selected from the group consisting of an ether bond, a urethane bond, a urea bond, an amide bond, an ester bond and a carbonate bond.
  • a linear group having 1 to 20 carbon atoms which may have at least one group selected from the group consisting of a group, a urethane bond, a urea bond, an amide bond, an ester bond, a carbonate bond, and an aromatic group
  • Q 1 is a nitrogen atom
  • Z in Formula I is a single bond, an arylene group, —C ( ⁇ O) —NH— or —C ( ⁇ O) —O— from the viewpoint of resolution, retention time-dependent inhibition, and ease of synthesis. It is preferably an arylene group or —C ( ⁇ O) —O—, more preferably —C ( ⁇ O) —NH— or —C ( ⁇ O) —O—.
  • Z in Formula II is preferably a single bond, an arylene group, or —C ( ⁇ O) —O—, and is a single bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. Is more preferable.
  • R 2 in Formula I has at least one group selected from the group consisting of an ether bond, a urethane bond, and a urea bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. It is preferably a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and has at least one group selected from the group consisting of an ether bond, a urethane bond and a urea bond. It is more preferably a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms, particularly preferably a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms.
  • R 2 in Formula II is preferably a single bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis.
  • R 3 and R 4 in Formula I are each independently a hydrogen atom or a carbon number of 1 that may have an ether bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. It is preferably a linear, branched or cyclic alkyl group of ⁇ 20, more preferably a hydrogen atom or a linear, branched or cyclic alkyl group of 1 to 20 carbon atoms.
  • R 2 , R 3 and R 4 in the formula I are combined to form a nitrogen-containing aliphatic ring is preferable, An embodiment in which a piperidine ring is formed is more preferable.
  • Q 1 in Formula II is preferably a nitrogen-containing heteroaromatic group from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis, and is pyridyl, methylpyridyl, imidazolyl, methylimidazolyl Group or a triazolyl group is more preferable, a pyridyl group is more preferable, and a 4-pyridyl group is particularly preferable.
  • the monomer that forms a structural unit having a pKaH group of 3 or more include the following monomers. 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2- (dimethylamino) ethyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2,2 methacrylate , 6,6-tetramethyl-4-piperidyl, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2- (diethylamino) ethyl methacrylate, 2- (dimethylamino) ethyl acrylate, acrylic acid 2- (diethylamino) ethyl, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate, N- (3-diethylamino) propyl methacrylate, N- (3-diethylamino acrylate)
  • the structural unit having a pKaH group of 3 or more contained in the polymer A may be only one type or two or more types.
  • the polymer A is preferably 0.01% by mass or more and 10% by mass or less of structural units having a pKaH group of 3 or more with respect to the total mass of the polymer A. More preferably, it is 0.05 mass% or more and 8 mass% or less, More preferably, it is 0.1 mass% or more and 5 mass% or less, It is especially preferable that it is 0.4 mass% or more and 4 mass% or less, Most preferably, it is 0.6 mass% or more and 2 mass% or less.
  • the content (content ratio: mass ratio) of the structural unit having a pKaH group of 3 or more in the polymer A can be confirmed by the intensity ratio of the peak intensity calculated by 13 C-NMR measurement by a conventional method. .
  • the polymer disclosed in the present disclosure is a structural unit other than the structural unit having an acid group protected with an acid-decomposable group, the structural unit having an acid group, and the structural unit having a basic group.
  • the photosensitive transfer material according to the present invention may be included within a range that does not impair the effect.
  • styrenes (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid Diester, bicyclounsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride, group having aliphatic cyclic skeleton, other Mention may be made of unsaturated compounds.
  • Various characteristics of the polymer can be adjusted by adjusting at least one of the type and content using other structural units. In particular, the Tg of the polymer can be easily adjusted to 90 ° C. or lower by appropriately using other structural units.
  • the polymer may contain only 1 type of other structural units, and may contain 2 or more types.
  • structural units having an aromatic ring or structural units having an aliphatic cyclic skeleton are preferable from the viewpoint of improving the electrical properties of the obtained transfer material.
  • monomers that form these structural units include styrene, tert-butoxystyrene, methylstyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, And benzyl (meth) acrylate etc. are mentioned.
  • the structural unit derived from a cyclohexyl (meth) acrylate is mentioned preferably.
  • (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion.
  • (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion.
  • Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • the content of other structural units is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less with respect to the total mass of the polymer A.
  • the lower limit may be 0% by mass, but is preferably 1% by mass or more, and more preferably 5% by mass or more. Within the above range, the resolution and adhesion are further improved.
  • the preferable example of the polymer A in this indication is given, this indication is not limited to the following illustrations.
  • the ratio of the structural unit and the weight average molecular weight in the following exemplary compounds are appropriately selected in order to obtain preferable physical properties.
  • the manufacturing method (synthesis method) of the polymer A is not particularly limited, for example, a polymerizable monomer for forming the structural unit represented by the formula A, and further having an acid group as necessary. It can synthesize
  • the photosensitive resin layer contains the polymer A in a proportion of 50% by mass to 99.9% by mass with respect to the total mass of the photosensitive resin layer, from the viewpoint of developing good adhesion to the substrate. Preferably, it is contained in a proportion of 70 to 98% by mass.
  • the photosensitive resin layer is a polymer other than the polymer F and the polymer A (“other polymers” as long as the effects of the photosensitive transfer material according to the present disclosure are not impaired. May be further included.).
  • content of another polymer is 50 mass with respect to the total content of the polymer F in the said photosensitive resin layer, the polymer A, and another polymer. % Or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.
  • the photosensitive resin layer may contain only one type of other polymer, or may contain two or more types.
  • polyhydroxystyrene can be used and are commercially available, such as SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer).
  • ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 above, manufactured by Toagosei Co., Ltd.
  • Joncryl 690, Joncryl 6 Joncryl 67, Joncryl 586 manufactured by BASF or the like can also be used.
  • the photosensitive resin layer contains a photoacid generator.
  • the photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiation with actinic rays such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
  • the photoacid generator used in the present disclosure is preferably a compound that generates an acid in response to an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but its chemical structure is not limited.
  • a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can be used as a sensitizer as long as it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
  • the photoacid generator used in the present disclosure is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a pKa of 2 or less.
  • a photoacid generator that generates an acid is particularly preferable.
  • the lower limit value of pKa is not particularly defined, but is preferably ⁇ 10.0 or more, for example.
  • the photoacid generator examples include an ionic photoacid generator and a nonionic photoacid generator.
  • the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound described later from the viewpoint of sensitivity and resolution, and an oxime sulfonate compound. It is more preferable to contain.
  • the photoacid generator is preferably a photoacid generator that generates sulfonic acid, such as an oxime sulfonate compound, from the viewpoint of sensitivity and resolution.
  • nonionic photoacid generators examples include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
  • the photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion.
  • These photoacid generators can be used singly or in combination of two or more.
  • Specific examples of trichloromethyl-s-triazines and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP 2011-212494A.
  • oxime sulfonate compound that is, a compound having an oxime sulfonate structure
  • a compound having an oxime sulfonate structure represented by the following formula (B1) is preferable.
  • R 21 represents an alkyl group or an aryl group
  • * represents a bonding site with another atom or another group.
  • any group may be substituted, and the alkyl group in R 21 may be linear or branched. It may have a ring structure. Acceptable substituents are described below.
  • the alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • the alkyl group of R 21 is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or other bridged alicyclic group) , Preferably a bicycloalkyl group or the like), or a halogen atom.
  • the aryl group for R 21 is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a naphthyl group.
  • the aryl group of R 21 may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a halogen atom.
  • the compound having an oxime sulfonate structure represented by the formula (B1) is preferably an oxime sulfonate compound described in paragraphs 0078 to 0111 of JP-A-2014-85643.
  • Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, quaternary ammonium salts, and the like. Of these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.
  • ionic photoacid generators described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.
  • a photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
  • the content of the photoacid generator in the photosensitive resin layer is preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of sensitivity and resolution. More preferably, the content is 5% by mass to 5% by mass.
  • the photosensitive resin layer may further contain a basic compound.
  • the molecular weight of the basic compound in the present disclosure is preferably less than 2,000, and more preferably less than 1,000.
  • the basic compound can be arbitrarily selected from basic compounds used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include compounds described in JP-A-2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
  • aliphatic amine examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like.
  • examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
  • aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.
  • heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene and 1, And 8-diazabicyclo [
  • Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
  • Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
  • the said basic compound may be used individually by 1 type, or may use 2 or more types together.
  • the content of the basic compound in the photosensitive resin layer is 0.001% by mass to 5% by mass with respect to the total mass of the photosensitive resin layer. It is preferable that it is 0.01 mass% or more and 2 mass% or less, and it is still more preferable that it is 0.05 mass% or more and 1 mass% or less.
  • the said photosensitive resin layer in this indication can contain a well-known additive as needed besides the said component.
  • the photosensitive resin layer may contain at least one polymerization inhibitor.
  • the polymerization inhibitor for example, the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784 can be used. Of these, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.
  • the content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, and 0.01% by mass with respect to the total mass of the photosensitive resin layer. % To 1% by mass is more preferable, and 0.01% to 0.8% by mass is even more preferable.
  • the photosensitive resin layer may contain a solvent.
  • the photosensitive resin composition for forming the photosensitive resin layer is a photosensitive resin composition containing a solvent by adjusting the viscosity of the photosensitive resin composition once by adding a solvent in order to easily form the photosensitive resin layer.
  • the photosensitive resin composition can be applied and dried to suitably form the photosensitive resin layer.
  • a known solvent can be used as the solvent used in the present disclosure.
  • Solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers And diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones.
  • Specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP2011-212494A, the contents of which are incorporated herein.
  • the solvent which can be used for this indication may be used individually by 1 type, and it is more preferable to use 2 types together.
  • two or more solvents for example, combined use of propylene glycol monoalkyl ether acetates and dialkyl ethers, combined use of diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetates A combination with the above is preferred.
  • the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof. Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C.
  • propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), and An example is propylene glycol methyl-n-propyl ether (boiling point 131 ° C.).
  • Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate.
  • the content of the solvent in applying the photosensitive resin composition is preferably 50 parts by weight to 1,900 parts by weight, preferably 100 parts by weight to 100 parts by weight of the total solid content in the photosensitive resin composition. More preferably, it is 900 parts by mass.
  • the content of the solvent in the photosensitive resin layer is preferably 2% by mass or less, more preferably 1% by mass or less, and more preferably 0.5% by mass with respect to the total mass of the photosensitive resin layer. % Or less is more preferable.
  • the photosensitive resin layer may contain a plasticizer for the purpose of improving plasticity.
  • the plasticizer preferably has a weight average molecular weight smaller than that of the polymer A.
  • the weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, and still more preferably 800 or more and less than 4,000 from the viewpoint of imparting plasticity.
  • the plasticizer is not particularly limited as long as it is a compound that is compatible with the polymer A and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule.
  • the alkyleneoxy group contained in the plasticizer preferably has the following structure.
  • R represents an alkyl group having 2 to 8 carbon atoms
  • n represents an integer of 1 to 50
  • * represents a bonding site with another atom.
  • compound X a compound having an alkyleneoxy group having the above structure
  • the resin composition does not fall under the plasticizer in the present disclosure.
  • the optionally added surfactant is generally not used in an amount that brings plasticity to the photosensitive resin composition, and thus does not correspond to the plasticizer in the present specification.
  • plasticizer examples include, but are not limited to, compounds having the following structure.
  • the content of the plasticizer is preferably 1% by mass to 50% by mass and more preferably 2% by mass to 20% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of adhesion. preferable.
  • the said photosensitive resin layer may contain only 1 type of plasticizers, and may contain 2 or more types.
  • the photosensitive resin layer can further contain a sensitizer.
  • the sensitizer absorbs actinic rays and enters an electronically excited state.
  • the sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise
  • anthracene derivative a compound selected from the group consisting of an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a base styryl derivative, and a distyrylbenzene derivative is preferable, and an anthracene derivative is more preferable.
  • Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 1,10-dibromoanthracene, 2-ethylanthracene, or 9,10-dimethoxyanthracene is preferred.
  • Examples of the sensitizer include compounds described in paragraphs 0139 to 0141 of International Publication No. 2015/092731.
  • the content of the sensitizer is preferably 0% by mass to 10% by mass and more preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer.
  • the photosensitive resin layer in the present disclosure can include a heterocyclic compound.
  • a heterocyclic compound There is no restriction
  • Heterocyclic monomers having the following d electrons can be added.
  • the addition amount of the heterocyclic compound in the photosensitive resin layer is preferably 0.01% by mass to 50% by mass with respect to the total mass of the photosensitive resin layer when the heterocyclic compound is added.
  • the content is more preferably 0.1% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass. It is preferable in the said range from a viewpoint of adhesiveness and etching tolerance. Only 1 type may be used for a heterocyclic compound and it can also use 2 or more types together.
  • Specific examples of the compound having an epoxy group in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like.
  • a compound having an epoxy group in the molecule can be obtained as a commercial product.
  • JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Co., Ltd.), JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like commercially available products described in paragraph 0189 of JP2011-221494A, and the like can be mentioned.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and aliphatic epoxy resin is particularly preferable.
  • the compound containing an oxetanyl group is preferably used alone or mixed with a compound containing an epoxy group.
  • the heterocyclic compound is preferably a compound having an epoxy group from the viewpoint of etching resistance and line width stability.
  • the photosensitive resin layer may contain an alkoxysilane compound.
  • Preferred examples of the alkoxysilane compound include trialkoxysilane compounds.
  • Examples of the alkoxysilane compound include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltriacoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, and ⁇ -methacryloxy.
  • ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, ⁇ -glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used alone or in combination of two or more.
  • the photosensitive resin layer in the present disclosure includes metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, and ultraviolet absorption.
  • Known additives such as an agent, a thickener, a crosslinking agent, and an organic or inorganic suspending agent can be further added.
  • Preferred embodiments of the other components are described in JP-A-2014-85643, paragraphs 0165 to 0184, respectively, and the contents of this publication are incorporated herein.
  • the average film thickness of the photosensitive resin layer is preferably 1.0 ⁇ m or more, and more preferably 2.0 ⁇ m or more, from the viewpoint of transferability (laminate).
  • the average film thickness of the photosensitive resin layer is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, from the viewpoint of production suitability.
  • a photosensitive resin composition for forming a photosensitive resin layer can be prepared by mixing each component and a solvent in an arbitrary ratio and by an arbitrary method, and dissolving by stirring. For example, it is possible to prepare a composition by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent.
  • the composition prepared as described above can be used after being filtered using a filter having a pore size of 0.2 ⁇ m or the like.
  • the photosensitive transfer material according to the present disclosure having the photosensitive resin layer on the temporary support can be obtained by applying the photosensitive resin composition on the temporary support or an intermediate layer described later and drying the photosensitive resin composition.
  • the coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
  • the photosensitive resin layer can also be applied after forming other layers described later on the intermediate layer.
  • the photosensitive transfer material according to the present disclosure has an intermediate layer between the temporary support and the photosensitive resin layer from the viewpoint of pattern shape maintenance when the transferred photosensitive resin layer is aged after exposure. It is preferable. Moreover, it is preferable that the said intermediate
  • the binder is preferably a water-soluble or alkali-soluble binder, and more preferably a water-soluble or alkali-soluble polymer.
  • water-soluble means that the solubility in water at pH 7.0 is 0.1% by mass or more at 25 ° C.
  • alkali-soluble means pH 8. It means that the solubility in 5 or more alkaline aqueous solution is 0.1% by mass or more.
  • water-soluble or alkali-soluble may be either water-soluble or alkali-soluble, or may be water-soluble and alkali-soluble.
  • binder examples include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, or m- / p-mixed).
  • novolak resin such as mixed formaldehyde resin, pyrogallol acetone resin, polyhydroxystyrene resin, modified cellulose resin, acrylic resin having a hydroxy group (for example, hydroxyalkyl (meth) acrylate homopolymer or copolymer), Starches, glycogens, chitins, agaroses, carrageenans, pullulans, gum arabic, soya gum, polyamide resin, epoxy resin, polyacetal resin, acrylic resin, polystyrene resin, polyester Urethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyethyleneimine, polyallylamine, polyalkylene glycol, and the like.
  • novolak resin such as mixed formaldehyde resin, pyrogallol acetone resin, polyhydroxystyrene resin, modified cellulose resin, acrylic resin having a hydroxy group (for example, hydroxyalkyl (meth) acrylate homopolymer or copolymer
  • the binder is at least one selected from the group consisting of a novolak resin, a modified cellulose resin, and an acrylic resin having a hydroxy group from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation.
  • a resin is preferable, and at least one resin selected from the group consisting of a modified cellulose resin and an acrylic resin having a hydroxy group is more preferable.
  • the modified cellulose resin is preferably hydroxyalkylated cellulose from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation.
  • hydroxyalkylated cellulose examples include hydroxymethylcellulose, hydroxyethylcellulose, polyhydroxyethylated cellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, glyoxalized hydroxypropylmethylcellulose, hydroxypropylmethylcellulose phthalate and the like.
  • it is preferably at least one resin selected from the group consisting of hydroxypropylcellulose and hydroxypropylmethylcellulose, and is hydroxypropylmethylcellulose. It is more preferable.
  • the weight average molecular weight of the binder is preferably 1,000 or more from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer, pattern formation, solubility in the developer after exposure, and transferability. , Preferably from 100,000 to 100,000, more preferably from 10,000 to 50,000.
  • the intermediate layer may contain one kind of binder alone or two or more kinds.
  • the content of the binder in the intermediate layer is based on the adhesiveness between the intermediate layer and the photosensitive resin layer, pattern formation, solubility in the developer after exposure, and transferability, with respect to the total mass of the intermediate layer, It is preferably 10% by mass or more and 100% by mass or less, more preferably 20% by mass or more and 100% by mass or less, still more preferably 40% by mass or more and 100% by mass or less, and 65% by mass or more and 85% by mass. % Or less is particularly preferable.
  • the intermediate layer preferably contains particles from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer.
  • the above particles are preferably metal oxide particles or organic particles from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, and oxidation of an element selected from the group consisting of Si, Ti and Zr. More preferably, it is a physical particle or an organic particle.
  • the metal of the metal oxide particles in the present disclosure includes semimetals such as B, Si, Ge, As, Sb, and Te.
  • the metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B , Oxide particles containing atoms such as Al, Si, Ge, Sn, Pb, Sb, Bi, Te, etc. are preferred, silica, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide, or Antimony / tin oxide is more preferable, silica, titanium oxide, titanium composite oxide, or zirconium oxide is more preferable, and silica, titanium oxide, or zirconium oxide is particularly preferable.
  • organic resin particles are preferably exemplified.
  • the organic resin particles include homopolymers and copolymers of acrylic acid monomers such as acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, and cellulose polymers such as nitrocellulose, methylcellulose, ethylcellulose, and cellulose acetate.
  • a condensation polymer such as butadiene-styrene copolymer, a rubber-based thermoplastic polymer such as a butadiene-styrene copolymer, a polymer obtained by polymerizing and crosslinking a photopolymerizable or thermopolymerizable compound such as an epoxy compound, Min compounds and the like.
  • acrylic resin particles are preferable as the organic particles, and polymethyl methacrylate particles are more preferable.
  • the surface of these particles can be treated with an organic material or an inorganic material in order to impart dispersion stability.
  • the particles are preferably particles having a hydrophilic surface.
  • the surface of particles having a hydrophobic surface may be subjected to a hydrophilic treatment.
  • the arithmetic average particle size of the above particles is preferably 400 nm or less, more preferably 250 nm or less, further preferably 150 nm or less, from the viewpoint of adhesion between the intermediate layer and the photosensitive layer. Particularly preferred is 200 nm.
  • the method for measuring the arithmetic average particle diameter of particles in the present disclosure refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the maximum diameter is taken as the diameter.
  • the volume fraction of the particles in the intermediate layer (volume ratio of particles in the intermediate layer) is 5% to 90% with respect to the total volume of the intermediate layer from the viewpoint of adhesion between the intermediate layer and the photosensitive layer. It is preferably 10% to 80%, more preferably 15% to 70%, and particularly preferably 20% to 60%.
  • the intermediate layer in the present disclosure may contain a known additive as necessary in addition to the binder.
  • Other additives that can be suitably used for the photosensitive resin layer include other additives.
  • the average film thickness of the intermediate layer is preferably 0.3 ⁇ m to 10 ⁇ m, more preferably 0.3 ⁇ m to 5 ⁇ m, and more preferably 0.3 ⁇ m from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formability. ⁇ 2 ⁇ m is particularly preferred.
  • the average value is preferably measured and calculated at 10 points or more. Specific examples include surface shape measurement and cross-sectional optical microscope or electron microscope observation. In addition, Bruker's Dektak series can be suitably used for surface shape measurement. Moreover, a scanning electron microscope (SEM) can be used suitably for cross-sectional observation.
  • SEM scanning electron microscope
  • the method for forming the intermediate layer is not particularly limited, but each component and a solvent (preferably an aqueous solvent) are mixed at a predetermined ratio and in an arbitrary method, and dissolved by stirring to form the intermediate layer.
  • An intermediate layer forming composition can be prepared. For example, it is possible to prepare a composition by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent.
  • the composition prepared as described above can be used after being filtered using a filter having a pore size of 5 ⁇ m.
  • the aqueous solvent include water and water-soluble solvents such as alcohols.
  • the intermediate layer can be easily formed on the temporary support by applying the intermediate layer-forming composition to the temporary support and drying it.
  • the coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
  • an intermediate layer can be applied after forming other layers (for example, a thermoplastic resin layer or the like) described later on the temporary support.
  • the intermediate layer may have two or more layers.
  • each layer preferably contains a water-soluble or alkali-soluble binder.
  • the particles may be contained in a plurality of layers, but the adhesion between the intermediate layer and the photosensitive resin layer, and the temporary support and the intermediate layer From the viewpoint of adhesion, it is preferably contained in a layer in contact with the photosensitive resin layer.
  • the photosensitive transfer material according to the present disclosure may have a layer other than the temporary support, the intermediate layer, and the photosensitive resin layer (hereinafter, may be referred to as “other layer”).
  • other layers include a contrast enhancement layer, a cover film, and a thermoplastic resin layer.
  • the photosensitive transfer material according to the present disclosure preferably further includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer or the intermediate layer from the viewpoint of transferability.
  • the photosensitive transfer material according to the present disclosure may have a cover film for the purpose of protecting the photosensitive resin layer.
  • Preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP 2014-85643 A, and preferred embodiments of the other layers are described in paragraphs 0194 to 0196 of JP 2014-85643 A, respectively.
  • a thermoplastic resin layer contains the at least 1 sort (s) of thermoplastic resin chosen from the group which consists of an acrylic resin and a styrene / acryl copolymer from a transferable viewpoint.
  • the photosensitive transfer material according to the present disclosure has other layers such as a thermoplastic resin layer
  • the photosensitive transfer material is manufactured according to the method for manufacturing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138. can do.
  • a solution for thermoplastic resin layer
  • a coating solution prepared by adding a resin and an additive to a solvent that does not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer after applying a coating liquid) and drying to provide a thermoplastic resin layer (intermediate)
  • the layer composition is applied and dried to laminate the intermediate layer.
  • a photosensitive transfer material according to the present disclosure is obtained by further applying a photosensitive resin composition prepared using a solvent that does not dissolve the intermediate layer on the formed intermediate layer, and drying and laminating the photosensitive resin layer. Can be suitably produced.
  • a contrast enhancement layer is a material that absorbs light with respect to an exposure wavelength before exposure, but gradually decreases with exposure, that is, a material that increases light transmittance (photodecoloration). It is a layer containing a coloring pigment component).
  • photodecolorable dye components include diazonium salts, stilbazolium salts, arylnitroso salts, and the like.
  • a phenolic resin or the like is used as the film forming component.
  • the method for producing a resin pattern according to the present disclosure is not particularly limited as long as it is a method for producing a resin pattern using the photosensitive transfer material according to the present disclosure, but the photosensitive resin in the photosensitive transfer material according to the present disclosure.
  • the circuit wiring manufacturing method according to the present disclosure is not particularly limited as long as it is a circuit wiring manufacturing method using the photosensitive transfer material according to the present disclosure.
  • the substrate is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface.
  • photosensitive resin compositions are classified into a negative type in which a portion irradiated with actinic rays is left as an image and a positive type in which a portion not irradiated with actinic rays is left as an image due to differences in photosensitive systems.
  • the positive type by irradiating actinic rays, for example, to improve the solubility of the exposed portion using a photosensitive agent that generates acid upon irradiation with actinic rays, both the exposed and unexposed portions are exposed at the time of pattern exposure. If the pattern shape obtained is not cured and the substrate is defective, the substrate can be reused (reworked) by full exposure or the like.
  • the positive type is preferable from the viewpoint of excellent so-called reworkability.
  • the technique of reexposing the remaining photosensitive resin layer to produce a different pattern can be realized only by the photosensitive resin layer, the resin pattern manufacturing method according to the present disclosure or the circuit according to the present disclosure In the method for producing a wiring, an embodiment in which exposure is performed twice or more is preferable.
  • the method of manufacturing a resin pattern according to the present disclosure or the method of manufacturing a circuit wiring according to the present disclosure includes a substrate, preferably a conductive layer, as the outermost layer on the photosensitive resin layer side in the photosensitive transfer material according to the present disclosure. It is preferable to include the process (bonding process) of making it contact and bond to the board
  • the bonding step for example, in the case of a photosensitive transfer material having a temporary support, an intermediate layer, and a photosensitive resin layer (which may further have a cover film), the outermost layer on the transfer side Is a photosensitive resin layer, but another layer may be further formed on the photosensitive resin layer, and the outermost layer may be another layer.
  • the bonding step it is preferable that the outermost layer on the photosensitive resin layer side of the photosensitive transfer material is brought into contact with a substrate having a conductive layer on the surface for bonding. Moreover, in the said bonding process, it is preferable to crimp
  • the patterned photosensitive resin layer after exposure and development can be suitably used as an etching resist when the conductive layer is etched.
  • the photosensitive resin layer side of the photosensitive transfer material is overlaid on a substrate, and pressure is applied with a roll or the like, or pressure and heating are performed.
  • laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
  • the pressure and temperature of the bonding in the bonding step there are no particular limitations on the pressure and temperature of the bonding in the bonding step, and it depends on the surface material of the substrates to be bonded, for example, the material of the conductive layer, the material of the photosensitive resin layer, the conveyance speed, and the pressure bonding machine used. Can be set as appropriate.
  • the substrate used in the present disclosure is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface of a base material.
  • a wiring is formed by patterning the conductive layer.
  • several electroconductive layers such as a metal oxide and a metal, were provided in film base materials, such as a polyethylene terephthalate.
  • substrate used for this indication is a board
  • the said conductive layer is a layer containing copper from a viewpoint which exhibits the effect in this indication more.
  • the substrate is preferably a substrate in which a plurality of conductive layers are stacked on a support.
  • a support body is a glass substrate or a film base material, and it is more preferable that it is a film base material.
  • the support is particularly preferably a sheet-shaped resin composition.
  • the support is preferably transparent.
  • the refractive index of the support is preferably 1.50 to 1.52.
  • the support may be composed of a translucent substrate such as a glass substrate, and tempered glass represented by Corning's gorilla glass can be used.
  • materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.
  • a film substrate is used as the substrate, it is more preferable to use a substrate that is not optically distorted and a substrate having high transparency.
  • Specific examples of the material include polyethylene terephthalate (PET), Examples thereof include polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.
  • Examples of the conductive layer include any conductive layer used for general wiring or touch panel wiring.
  • Examples of the material for the conductive layer include metals and metal oxides.
  • Examples of the metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO 2 .
  • Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, and Mo.
  • At least one of the plurality of conductive layers includes a metal oxide.
  • the conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition part used in a capacitive touch panel or a wiring of a peripheral extraction part.
  • the manufacturing method of the resin pattern which concerns on this indication, or the manufacturing method of the circuit wiring which concerns on this indication includes the process (exposure process) of carrying out pattern exposure of the said photosensitive resin layer after the said bonding process.
  • the photosensitive resin layer is irradiated with actinic rays through a mask having a predetermined pattern.
  • the photoacid generator is decomposed to generate an acid.
  • the acid-decomposable group contained in the coating film component is hydrolyzed to produce an acid group, for example, a carboxy group or a phenolic hydroxyl group.
  • the detailed arrangement and specific size of the pattern are not particularly limited. Since it is desired to improve the display quality of a display device (for example, a touch panel) including an input device having a circuit board manufactured in the present disclosure and to minimize the area occupied by the extraction wiring, at least a part of the pattern (particularly the touch panel).
  • the electrode pattern and the part of the lead-out wiring) are preferably fine wires of 100 ⁇ m or less, and more preferably 70 ⁇ m 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 producing a resin pattern according to the present disclosure or the method for producing a circuit wiring according to the present disclosure includes a step of bringing the photosensitive transfer material and an exposure mask into contact between the bonding step and the exposure step. It is preferable to contain. It is excellent in the resolution of the pattern obtained as it is the said aspect.
  • Visible light, ultraviolet light, and an electron beam are mentioned as actinic light, However, Visible light or ultraviolet light is preferable and an ultraviolet-ray is especially preferable.
  • an exposure light source using actinic 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, etc. can be used.
  • Actinic rays having a wavelength of 300 nm to 450 nm, such as h-line (405 nm), can be preferably used.
  • irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
  • Exposure dose depending on the photosensitive resin layer to be used may be appropriately selected, but is preferably from 5mJ / cm 2 ⁇ 200mJ / cm 2, more preferably 10mJ / cm 2 ⁇ 100mJ / cm 2 . It is also preferable to perform heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure.
  • PEB Post Exposure Bake
  • pattern exposure performs after peeling a temporary support body from the photosensitive resin layer, before peeling a temporary support body, it exposes through a temporary support body, and peels a temporary support body after that. Also good.
  • the pattern exposure may be exposure through a mask or digital exposure using a laser or the like.
  • the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure includes a step of developing the exposed photosensitive resin layer to form a pattern after the exposing step (developing step). It is preferable to contain.
  • the photosensitive transfer material has an intermediate layer
  • the exposed intermediate layer is also removed together with the exposed photosensitive resin layer in the development step.
  • the intermediate layer in the unexposed area may also be removed in a form of being dissolved or dispersed in the developer.
  • Development of the exposed photosensitive resin layer in the development step can be performed using a developer.
  • the developer is not particularly limited as long as the exposed portion of the photosensitive resin layer can be removed.
  • a known developer such as the developer described in JP-A No.
  • the developer is preferably a developer in which the exposed portion of the photosensitive resin layer exhibits a dissolution type development behavior.
  • the developer is preferably an alkaline aqueous solution, and more preferably, for example, an alkaline aqueous solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L.
  • the developer may further contain an organic solvent miscible with water, a surfactant, and the like. Examples of the developer suitably used in the present disclosure include the developer described in Paragraph 0194 of International Publication No. 2015/092731.
  • the development method is not particularly limited, and any of paddle development, shower development, shower and spin development, dip development, and the like may be used.
  • the shower development will be described.
  • the exposed portion can be removed by spraying the developer onto the exposed photosensitive resin layer by shower. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
  • the liquid temperature of the developer is preferably 20 ° C. to 40 ° C. Moreover, the effect which suppresses the deformation
  • a method for manufacturing a resin pattern according to the present disclosure or a method for manufacturing a circuit wiring according to the present disclosure includes a step of washing with water after development, a step of drying a substrate having the obtained pattern, and the like. These steps may be included.
  • the post-baking process which heat-processes the pattern obtained by image development.
  • the post-baking is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably in an environment of 50.66 kPa or more. On the other hand, it is more preferable to carry out in an environment of 111.46 kPa or less, and it is particularly preferable to carry out in an environment of 101.3 kPa or less.
  • the post-baking temperature is preferably 80 ° C. to 250 ° C., more preferably 110 ° C. to 170 ° C., and particularly preferably 130 ° C. to 150 ° C.
  • the post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
  • the post-bake may be performed in an air environment or a nitrogen substitution environment.
  • the transport speed of the support in each step of the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure is not particularly limited. It is preferably from min to 10 m / min, and more preferably from 2.0 m / min to 8.0 m / min except during exposure.
  • the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure peels off the temporary support after the step of bonding to the substrate and before the step of forming the pattern. It is preferable to include a process (peeling process).
  • the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure uses the photosensitive transfer material. Therefore, after the photosensitive transfer material is bonded to each other and at any timing before development, Even if the support is peeled off, the adhesiveness with the photosensitive resin layer is excellent, so that the cause of defects such as partial peeling is suppressed, and the pattern can be formed satisfactorily.
  • the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure includes a step of bonding the substrate to the substrate and the photosensitive resin layer from the viewpoint of pattern formability and resolution. It is more preferable that a step of peeling the temporary support is included before the pattern exposure step. Further, in the case of the above-described aspect, when pattern exposure is performed with a mask in contact, the photosensitive resin layer and the mask are not in direct contact with each other, so that the pattern formability and resolution are excellent. There is no restriction
  • the circuit wiring manufacturing method preferably includes a step (etching step) of etching the conductive layer in a region where the pattern is not disposed.
  • the conductive layer is etched using the pattern formed from the photosensitive resin layer in the developing step as an etching resist.
  • Etching of the conductive layer can be performed by a known method such as a method described in paragraphs 0048 to 0054 of JP 2010-152155 A or a dry etching method such as a known plasma etching.
  • a known method such as a method described in paragraphs 0048 to 0054 of JP 2010-152155 A
  • a dry etching method such as a known plasma etching.
  • a commonly performed wet etching method in which the substrate is immersed in an etching solution can be used.
  • an acid type or alkaline type etchant may be appropriately selected in accordance with an object to be etched.
  • Acidic etchants include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, aqueous solutions of acidic components such as phosphoric acid, acidic components and ferric chloride, ammonium fluoride, or permanganese Examples thereof include a mixed aqueous solution of a salt such as potassium acid.
  • the acidic component a component obtained by combining a plurality of acidic components may be used.
  • Alkali type etching solutions include sodium hydroxide, potassium hydroxide, ammonia, organic amines, or aqueous solutions of alkali components such as organic amine salts such as tetramethylammonium hydroxide, alkaline components and potassium permanganate.
  • alkali components such as organic amine salts such as tetramethylammonium hydroxide, alkaline components and potassium permanganate.
  • a mixed aqueous solution of a salt such as As the alkali component, a component obtained by combining a plurality of alkali components may be used.
  • the temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower.
  • the pattern used as an etching mask preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower. Therefore, the pattern is prevented from peeling off during the etching process, and a portion where the pattern does not exist is selectively etched.
  • a process of cleaning the etched substrate (cleaning process) and a process of drying the etched substrate (drying process) are performed as necessary. Also good.
  • the cleaning step for example, the substrate may be cleaned with pure water for 10 seconds to 300 seconds at room temperature (10 ° C. to 35 ° C.).
  • the drying step for example, air blow may be used, and the air blow pressure (about 0.1 kg / cm 2 to about 5 kg / cm 2 ) may be appropriately adjusted for drying.
  • the manufacturing method of the circuit wiring which concerns on this indication includes the process (etching resist peeling process) which peels the said photosensitive resin layer using peeling liquid after the said etching process. After the etching process is finished, the patterned photosensitive resin layer remains. If the photosensitive resin layer is unnecessary, all the remaining photosensitive resin layers may be removed.
  • a method of peeling using a peeling solution for example, a substrate having the above-mentioned photosensitive resin layer or the like in the peeling solution preferably stirred at 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 5 minutes. Examples include a method of immersing for ⁇ 30 minutes.
  • an inorganic alkali component such as sodium hydroxide or potassium hydroxide, or an organic alkali component such as a tertiary amine or quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or And a stripping solution dissolved in a mixed solution thereof.
  • a stripping solution may be used and stripped by a spray method, a shower method, a paddle method, or the like.
  • the manufacturing method of the circuit wiring which concerns on this indication may repeat an exposure process, a image development process, and an etching process twice or more as needed.
  • the exposure step, the development step, and other steps in the present disclosure the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present disclosure.
  • the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure may include other optional steps.
  • the following processes are mentioned, it is not limited to these processes.
  • the manufacturing method of the circuit wiring according to the present disclosure may include a process of reducing the visible light reflectivity of the surface of the conductive layer, for example, a part or all of the surface of the conductive layer on the substrate.
  • the treatment for reducing the visible light reflectance include an oxidation treatment.
  • the visible light reflectance can be reduced by blackening the copper by oxidizing copper.
  • paragraphs 0017 to 0025 of JP2014-150118A, and paragraphs 0041, 0042, 0048 and 0058 of JP2013-206315A are described. The contents of this publication are incorporated herein.
  • a method of manufacturing a circuit wiring according to the present disclosure includes a step of forming an insulating film on the substrate, for example, a formed wiring (etched conductive layer), and a step of forming a new conductive layer on the insulating film. It is also preferable to contain.
  • an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.
  • a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
  • the new conductive layer may be etched by forming an etching resist by a method similar to the above, or may be separately etched by a known method.
  • the substrate having the circuit wiring obtained by the circuit wiring manufacturing method according to the present disclosure may have only one layer of wiring on the substrate, or may have two or more layers of wiring.
  • the substrate may have a plurality of conductive layers on both surfaces, and the circuit may be sequentially or simultaneously formed on the conductive layers formed on both surfaces of the substrate.
  • a wiring in which a first conductive pattern (first wiring) is formed on one surface of the substrate and a second conductive pattern (second wiring) is formed on the other surface, preferably a touch panel wiring. can be formed.
  • the circuit wiring according to the present disclosure is a circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure.
  • substrate which has the circuit wiring which concerns on this indication is a board
  • substrate which has the circuit wiring which concerns on this indication is not limited, For example, it is preferable that it is a circuit wiring board for touchscreens.
  • the input device is mentioned as an apparatus provided with the circuit wiring manufactured by the manufacturing method of the circuit wiring concerning this indication.
  • the input device according to the present disclosure may be an input device having at least a circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure, and is preferably a capacitive touch panel.
  • the display device according to the present disclosure preferably includes the input device according to the present disclosure.
  • the display device according to the present disclosure is preferably an organic EL display device and an image display device such as a liquid crystal display device.
  • the touch panel according to the present disclosure is a touch panel having at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure.
  • the touch panel according to the present disclosure preferably includes at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
  • the touch panel display device according to the present disclosure is a touch panel display device having at least circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure, and is preferably a touch panel display device including the touch panel according to the present disclosure.
  • the touch panel manufacturing method according to the present disclosure is not particularly limited as long as it is a touch panel manufacturing method using the photosensitive transfer material according to the present disclosure, but the photosensitive resin of the photosensitive transfer material according to the present disclosure.
  • a step of bringing the outermost layer on the layer side into contact with a substrate having a conductive layer, a step of pattern-exposing the photosensitive resin layer, and a step of 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 disposed are preferably included in this order.
  • any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used.
  • the electrostatic capacity method is preferable.
  • a so-called in-cell type for example, those described in FIGS. 5, 6, 7, and 8 of JP-T-2012-517051
  • a so-called on-cell type for example, JP 2013-168125 A
  • OGS One Glass Solution
  • TOL Touch-on-Lens
  • other configurations for example, those shown in FIG. 6 of JP2013-164671A
  • various out-cell types for example, GG, G1, G2, GFF, GF2, GF1, G1F, etc.
  • ATHF 2-tetrahydrofuranyl acrylate (synthetic product)
  • MATHF 2-tetrahydrofuranyl methacrylate (synthetic product)
  • TBA tert-butyl acrylate (Fuji Film Wako Pure Chemical Industries, Ltd.)
  • AA Acrylic acid (Fuji Film Wako Pure Chemical Industries, Ltd.)
  • EA ethyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
  • MMA Methyl methacrylate (Fuji Film Wako Pure Chemical Industries, Ltd.)
  • CHA cyclohexyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
  • PMPMA 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • DPMA 1,2,2,6,6-
  • ⁇ Photo acid generator> B-1 Compound having the structure shown below (Compound described in paragraph 0227 of JP 2013-47765 A, synthesized according to the method described in paragraph 0227)
  • Ts represents a tosyl group.
  • B-4 GSID-26-1, triarylsulfonium salt (manufactured by BASF, the following compound)
  • Polymer C-10 Compound having the structure shown below (I / O value: 0.41, Tg: -35 ° C., fluorine atom content: 11%, the numerical value on the lower right of [] is the mass of the structural unit) (The ratio represents the number of repetitions.)
  • Polymer C-11 Compound having the structure shown below (I / O value: 0.29, Tg: 15 ° C., fluorine atom content: 27%, the numerical value on the lower right of [] is the mass ratio of structural units Represents.)
  • Example 1 ⁇ Preparation of photosensitive resin composition 1> The photosensitive resin composition 1 was produced with the following prescription.
  • Polymer A1 Polymer A
  • Photoacid generator above B-1: 2.0 parts
  • Polymer C-1 Polymer F
  • Base Compound above D-2: 0.3 part
  • PGMEA 900 parts
  • the photosensitive resin composition 1 On a polyethylene terephthalate film (hereinafter also referred to as PET (A)) having a thickness of 25 ⁇ m serving as a temporary support, the photosensitive resin composition 1 is dried to a thickness of 3.0 ⁇ m using a slit nozzle. It was applied as follows. After that, it was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (Tradegar, OSM-N) was pressure-bonded as a cover film (protective film), and the photosensitive transfer material of Example 1 (dry film resist) was made.
  • PET polyethylene terephthalate film
  • the intermediate layer composition 1 was slit-coated on a polyethylene terephthalate film having a thickness of 25 ⁇ m serving as a temporary support so as to have a dry film thickness of 2.0 ⁇ m, and dried in a convection oven at 100 ° C. for 2 minutes.
  • the photosensitive resin composition 1 was applied onto the intermediate layer using a slit nozzle so that the dry film thickness was 3.0 ⁇ m. Then, it was dried in a convection oven at 100 ° C. for 2 minutes, and finally a polyethylene film (Tradegar, OSM-N) was pressure-bonded as a cover film (protective film), and the photosensitive transfer material of Example 2 (dry film resist) was made.
  • Examples 3 and 4 and Comparative Example 2 Photosensitivity was obtained in the same manner as in Example 2 except that the composition of the photosensitive resin composition was changed so that the polymer A, photoacid generator, polymer F, and basic compound used were as shown in Table 3. A transfer material was prepared.
  • Example 10 A photosensitive transfer material was produced in the same manner as in Example 2 except that the following photosensitive resin composition 2 and the following intermediate layer composition 2 were used.
  • the photosensitive resin composition 2 was obtained by preparing with the following composition and filtering with the filter made from a polytetrafluoroethylene with a hole diameter of 0.2 micrometer.
  • Polymer A4 (Polymer A): 93.9 parts
  • Photoacid generator (above B-1): 2.0 parts
  • Polymer C-2 (Polymer F): 0.1 parts
  • PGMEA 900 Part
  • An intermediate layer composition 2 was prepared according to the following formulation. -Distilled water: 13.4 parts-Methanol: 75.6 parts-Hydroxymethylcellulose (trade name: HPC-SSL, manufactured by Nippon Soda Co., Ltd.) 4.1 parts-Snowtex O (silica particles, manufactured by Nissan Chemical Industries, arithmetic average particle size 12 nm): 68.5 parts
  • Photosensitivity was obtained in the same manner as in Example 1 except that the composition of the photosensitive resin composition was changed so that the polymer A, photoacid generator, polymer F, and basic compound used were as shown in Table 3. A transfer material was prepared.
  • Example 2 except that the composition of each composition was changed so that the polymer A, the photoacid generator, the polymer F, the basic compound, and the intermediate layer composition used were as shown in Table 3. In the same manner, a photosensitive transfer material was produced.
  • PET polyethylene terephthalate
  • the cover film was peeled from the produced photosensitive transfer material, and was laminated on the PET substrate with a copper layer under the lamination conditions of a roll temperature of 100 ° C., a linear pressure of 0.6 MPa, and a linear velocity (laminate velocity) of 3.6 m / min. Thereafter, the sample was pressurized in an autoclave at 50 ° C. for 3 hours under the condition of 0.6 MPa.
  • the temporary support was peeled off and developed for 5 hours after exposure with an ultra-high pressure mercury lamp through a 10 ⁇ m line width and space pattern (Duty ratio 1: 1) mask without peeling off the temporary support. Development was performed by shower development using a 1.0% aqueous sodium carbonate solution at 25 ° C.
  • a 10 ⁇ m line-and-space pattern was formed by the above-described method, an exposure amount at which the ratio of the line width to the space width was 1: 1 was determined, and a sample was patterned with the exposure amount.
  • the side wall portions on both sides are projected with a scanning electron microscope (SEM), and the number of dimples is counted in the obtained SEM image (magnification 5,000 times, tilt 20 °). did.
  • SEM scanning electron microscope
  • the number of dimples was counted, and the number of dimples existing in one pattern was averaged and evaluated according to the following criteria. Three or more are practical levels. 5: 0 More than 4: 0 Less than 2 3: More than 2 Less than 4 2: More than 4 Less than 8 1: More than 8
  • Table 3 summarizes the evaluation results in each example and each comparative example.
  • the photosensitive transfer materials of Examples 1 to 24 are superior to the photosensitive transfer materials of Comparative Examples 1 to 4 in terms of dimple suppression of the resulting pattern and the surface condition upon application. Further, from Table 3 above, the photosensitive transfer materials of Examples 1 to 24 are excellent in storage stability (pattern formation property after long-term storage of the photosensitive transfer material).
  • Example 101 On the 100 ⁇ m-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer at a thickness of 200 nm by vacuum evaporation. Thus, a circuit forming substrate was obtained.
  • the photosensitive transfer material obtained in Example 1 was laminated on the copper layer (Lamiroll temperature 120 ° C., linear pressure 0.8 MPa, linear velocity 1.0 m / min.).
  • a photomask provided with a pattern hereinafter also referred to as “pattern A”) shown in FIG. 2 having a structure in which conductive layer pads are connected in one direction without peeling off the temporary support from the laminated support is used.
  • the contact pattern was exposed.
  • the solid line portion SL and the gray portion G are light shielding portions, and the dotted line portion DL virtually shows an alignment alignment frame.
  • the temporary support was peeled off, developed and washed with water to obtain a pattern A.
  • the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), A substrate on which both copper and ITO were drawn in pattern A was obtained.
  • pattern alignment was performed using a photomask provided with openings of a pattern shown in FIG.
  • pattern B in the aligned state, and development and washing were performed.
  • the gray portion G is a light shielding portion
  • the dotted line portion DL is a virtual alignment alignment frame.
  • the copper layer was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
  • KP-301 manufactured by Kanto Chemical Co., Inc.
  • Example 102 On the 100 ⁇ m-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer at a thickness of 200 nm by vacuum evaporation. Thus, a circuit forming substrate was obtained.
  • the photosensitive transfer material obtained in Example 1 was unwound and laminated on the copper layer (roll temperature 120 ° C., linear pressure 0.8 MPa, linear velocity 1.0 m / min.).
  • the laminated support was subjected to pattern exposure using a photomask provided with a pattern A having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support.
  • the temporary support was peeled off, developed and washed with water to obtain a pattern A.
  • the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), A substrate on which both copper and ITO were drawn in pattern A was obtained.
  • PET (A) was laminated as a protective layer on the remaining resist. In this state, pattern exposure was performed using a photomask provided with an opening of pattern B in the aligned state, and after developing PET (A), development and washing were performed.
  • the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was stripped using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
  • a stripping solution KP-301 manufactured by Kanto Chemical Co., Inc.
  • Example 103 On the 100 ⁇ m-thick cycloolefin polymer (COP) substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer by a thickness of 200 nm by vacuum evaporation. To form a substrate for forming a conductive pattern.
  • the photosensitive transfer material obtained in Example 2 was bonded to a substrate on a copper layer (roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.) To obtain a laminate.
  • the laminate was subjected to pattern exposure using a photomask provided with a pattern A having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a resin pattern drawn with pattern A.
  • the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), and a peeling solution.
  • KP-301 manufactured by Kanto Chemical Co., Inc.
  • the photosensitive transfer material obtained in Example 2 was bonded onto the remaining resist (roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.).
  • pattern exposure was performed using a photomask provided with openings of pattern B in the aligned state, and the temporary support of the photosensitive transfer material was peeled off, followed by development and washing with water.
  • the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board having a conductive pattern. .
  • KP-301 manufactured by Kanto Chemical Co., Inc.

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  • General Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Human Computer Interaction (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne : un matériau de transfert photosensible comportant un support temporaire et une couche de résine photosensible, la couche de résine photosensible contenant un polymère A qui contient une unité constitutive présentant un groupe acide protégé par un groupe dégradable par un acide, un photogénérateur d'acide, et un polymère F qui contient une unité constitutive présentant un atome de fluor, la teneur en atome de fluor dans le polymère F étant de 20 à 50 % en masse inclus par rapport à la masse totale du polymère F, et le polymère F satisfaisant l'exigence f1 et/ou l'exigence f2 ; et un procédé de production d'un motif de résine, un procédé de fabrication d'un câblage de circuit, et un procédé de fabrication d'un panneau tactile, faisant chacun appel au matériau de transfert photosensible. f1 : la valeur E/S du polymère F est de 0,45 ou plus ; et f2 : la valeur E/S du polymère F est inférieure à 0,45 et le polymère F contient une unité constitutive présentant un groupe acide ou un groupe basique.
PCT/JP2019/018815 2018-05-22 2019-05-10 Matériau de transfert photosensible, procédé de production de motif de résine, procédé de fabrication de câblage de circuit, et procédé de fabrication de panneau tactile WO2019225363A1 (fr)

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JP2020521157A JPWO2019225363A1 (ja) 2018-05-22 2019-05-10 感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法

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JP2017156735A (ja) * 2016-02-26 2017-09-07 富士フイルム株式会社 感光性転写材料及び回路配線の製造方法
WO2017213056A1 (fr) * 2016-06-10 2017-12-14 富士フイルム株式会社 Procédé de fabrication d'un substrat à motif, et procédé de fabrication d'une carte de circuit imprimé
JP2018031847A (ja) * 2016-08-23 2018-03-01 富士フイルム株式会社 感光性転写材料、及び、回路配線の製造方法

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JP2008256735A (ja) * 2007-03-30 2008-10-23 Fujifilm Corp 感光性組成物、感光性転写材料、表示装置用遮光膜及びその形成方法、遮光膜付基板、表示装置、並びにパターン欠け防止方法
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JP2017156735A (ja) * 2016-02-26 2017-09-07 富士フイルム株式会社 感光性転写材料及び回路配線の製造方法
WO2017213056A1 (fr) * 2016-06-10 2017-12-14 富士フイルム株式会社 Procédé de fabrication d'un substrat à motif, et procédé de fabrication d'une carte de circuit imprimé
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