WO2019187364A1 - Matériau de transfert photosensible, procédé de production d'un motif de réserve, procédé de production de ligne de câblage de circuit, panneau tactile et dispositif d'affichage à écran tactile - Google Patents

Matériau de transfert photosensible, procédé de production d'un motif de réserve, procédé de production de ligne de câblage de circuit, panneau tactile et dispositif d'affichage à écran tactile Download PDF

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WO2019187364A1
WO2019187364A1 PCT/JP2018/044987 JP2018044987W WO2019187364A1 WO 2019187364 A1 WO2019187364 A1 WO 2019187364A1 JP 2018044987 W JP2018044987 W JP 2018044987W WO 2019187364 A1 WO2019187364 A1 WO 2019187364A1
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group
transfer material
photosensitive resin
layer
resin layer
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PCT/JP2018/044987
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English (en)
Japanese (ja)
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晃男 片山
漢那　慎一
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富士フイルム株式会社
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Priority to JP2020509631A priority Critical patent/JP7011046B2/ja
Publication of WO2019187364A1 publication Critical patent/WO2019187364A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/36—Chemically modified polycondensates by etherifying
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • 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 resist pattern manufacturing method, a circuit wiring manufacturing method, a touch panel, and a touch panel display device.
  • a display device such as an organic electroluminescence (EL) display device and a liquid crystal display device
  • a touch panel such as a capacitive input device
  • an electrode pattern corresponding to a sensor of a visual recognition part a peripheral wiring portion
  • a take-out wiring portion A conductive layer pattern such as wiring 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.
  • Japanese Patent No. 2832409 discloses at least (1) a support, (2) an intermediate layer having a film thickness of 0.1 to 5 ⁇ m provided on the support, and (3) provided on the intermediate layer.
  • a photopolymerizable resin material comprising a photopolymerizable resin layer containing a carboxyl group-containing binder, wherein the intermediate layer contains hydroxypropylmethylcellulose is disclosed.
  • JP-A-2016-57632 discloses (A) a novolak-type phenol resin obtained from metacresol and para-cresol, (B) a novolac-type phenol resin obtained from ortho-cresol, and (C) an acid generated by light. And a positive photosensitive resin composition containing the compound.
  • the substrate, the positive photosensitive resin layer, and the temporary support are formed by attaching the photosensitive transfer material to the substrate.
  • a laminate having at least this order is formed.
  • the positive photosensitive resin layer is developed to form a resist pattern.
  • a photomask having a pattern on the surface of the laminate from which the temporary support is peeled It has been studied to perform exposure (also referred to as “contact exposure”) by bringing it into contact with only a “mask”.
  • a problem to be solved by an embodiment according to the present disclosure is to provide a photosensitive transfer material in which contamination of a photomask during contact exposure is suppressed.
  • Another problem to be solved by another embodiment of the present disclosure is to provide a resist pattern manufacturing method, a circuit wiring manufacturing method, a touch panel, and a touch panel display device using the photosensitive transfer material. is there.
  • Means for solving the above problems include the following aspects. ⁇ 1> a temporary support; The middle layer, A positive photosensitive resin layer in this order, The temporary support and the intermediate layer are in contact with each other; The indentation hardness on the surface of the intermediate layer on the side in contact with the temporary support is 5.0 mN or more. Photosensitive transfer material. ⁇ 2> The photosensitive transfer material according to ⁇ 1>, wherein the intermediate layer contains a cellulose ether compound. ⁇ 3> The above ⁇ 1> or ⁇ 2 wherein the intermediate layer includes two or more layers, and the layer in contact with the positive photosensitive resin layer among the layers included in the intermediate layer includes a cellulose ether compound. > Photosensitive transfer material.
  • ⁇ 4> The above-mentioned ⁇ 3>, wherein the layer in contact with the temporary support in the intermediate layer contains hydroxypropyl methylcellulose, and the layer in contact with the positive photosensitive resin layer in the intermediate layer contains hydroxypropylcellulose.
  • ⁇ 6> The photosensitive transfer material according to ⁇ 5>, wherein the structural unit having an acid group protected with an acid-decomposable group includes a structural unit represented by any one of the following formulas A1 to A3.
  • R 11 and R 12 each independently represents a hydrogen atom, an alkyl group or an aryl group, at least one of R 11 and R 12 is an alkyl group or an aryl group, and R 13 is an alkyl group or Represents an aryl group, R 11 or R 12 and R 13 may be linked to form a cyclic ether, R 14 represents a hydrogen atom or a methyl group, and X 1 represents a single bond or a divalent linking group.
  • R 15 represents a substituent, and n represents an integer of 0 to 4.
  • R 21 and R 22 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 21 and R 22 is an alkyl group or an aryl group, and R 23 is an alkyl group or Represents an aryl group, and R 21 or R 22 and R 23 may combine to form a cyclic ether, and each R 24 independently represents a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, Represents an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.
  • 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, 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, X 0 represents a single bond or an arylene group, Y represents —S— or —O—.
  • 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 R 31 or R 32 and R 33 may be linked to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or an arylene group.
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group R 31 or R 32 and R 33 may be linked to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or an arylene group.
  • a touch panel comprising circuit wiring produced using the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 7> above.
  • a touch panel display device comprising the touch panel according to ⁇ 10>.
  • the manufacturing method of the resist pattern using the said photosensitive transfer material can be provided.
  • FIG. 1 is a schematic diagram illustrating an example of a layer configuration of a photosensitive transfer material according to the present disclosure.
  • FIG. 2 is a schematic diagram showing the pattern A.
  • FIG. 3 is a schematic diagram showing the pattern B.
  • symbol may be abbreviate
  • 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).
  • 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.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical description.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • “(meth) acrylic acid” is a concept including both acrylic acid and methacrylic acid
  • “(meth) acrylate” is a concept including both acrylate and methacrylate
  • the “) acryloyl group” is a concept including both an acryloyl group and a methacryloyl group.
  • the amount of each component in a layer such as a positive photosensitive resin layer is such that when a plurality of substances corresponding to each component are present in the layer, the plurality of substances present in the layer unless otherwise specified. Means the total amount.
  • the term “process” in the present disclosure is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, it is included in this term if the intended purpose of the process is achieved. It is.
  • “mass%” and “wt%” 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 (both trade names manufactured by Tosoh Corporation) unless otherwise specified.
  • the molecular weight was detected by a gel permeation chromatography (GPC) analyzer using a solvent THF (tetrahydrofuran) and a differential refractometer and converted using polystyrene as a standard substance.
  • GPC gel permeation chromatography
  • HLC registered trademark
  • TSKgel registered trademark
  • Super HZM-M 4.6 mm ID ⁇ 15 cm, Tosoh was used as a column.
  • Super HZ4000 (4.6 mm ID ⁇ 15 cm, manufactured by Tosoh Corporation)
  • Super HZ3000 (4.6 mm ID ⁇ 15 cm, manufactured by Tosoh Corporation)
  • Super HZ2000 (4.6 mm ID ⁇ 15 cm, Tosoh Corporation)
  • THF tetrahydrofuran
  • the calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “ It can be produced using any of the seven samples of “A-2500” and “A-1000”.
  • the total solid content means the total mass of components excluding volatile components such as a solvent in the composition.
  • the ratio of the structural unit in the resin represents a mass-weight ratio unless otherwise specified.
  • the molecular weight when there is a molecular weight distribution represents a weight average molecular weight (Mw) unless otherwise specified.
  • light is a concept including active energy rays such as ⁇ rays, ⁇ rays, electron beams, ultraviolet rays, visible rays, and infrared rays.
  • the “exposure” in the present disclosure is not limited to exposure using an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, EUV (Extreme ultraviolet) light, etc. And exposure with particle beams such as an ion beam.
  • the photosensitive transfer material according to the present disclosure has a temporary support, an intermediate layer, and a positive photosensitive resin layer in this order, and the temporary support and the intermediate layer are in contact with each other.
  • the indentation hardness on the surface of the layer in contact with the temporary support is 5.0 mN or more.
  • the present inventors have found that when contact exposure is performed using a photosensitive transfer material described in Japanese Patent No. 2832409 or Japanese Patent Application Laid-Open No. 2016-57632, contamination of the mask may occur.
  • the photosensitive transfer material described in Japanese Patent No. 2832409 is a photosensitive transfer material having a negative photosensitive resin layer, and is softer than a photosensitive transfer material having a positive photosensitive resin layer. Tends to be low. Further, when the photomask and the intermediate layer are bonded at the time of contact exposure, the photosensitive resin layer is peeled off from the substrate when the photomask is peeled off, and the components of the intermediate layer and the photosensitive resin layer are disclosed in JP-A-2016-57632.
  • the photosensitive transfer material described in 1 includes a positive photosensitive resin layer, but does not have a high-hardness intermediate layer, so that plastic deformation of the photosensitive transfer material is difficult to be suppressed, and is included in the positive photosensitive resin layer. Contamination of the mask with components may occur. Therefore, as a result of intensive studies, the present inventors have found that the photosensitive transfer material according to the present disclosure has an intermediate layer having an indentation hardness of 5.0 mN or more on the surface in contact with the temporary support, thereby allowing contact exposure. It was found that the contamination of the mask at the time was suppressed. This is presumably because the indentation hardness of the intermediate layer is the above value, thereby suppressing plastic deformation of the photosensitive transfer material during contact exposure.
  • an advantage of performing contact exposure is that the shape of the resist pattern obtained after development is good.
  • the inventors of the present invention as is conventionally performed, when a mask is placed on a temporary support and exposure is performed, a reflected wave generated by reflection of exposure light at the interface of the substrate or the positive photosensitive resin layer. It was found that the photosensitive resin layer was exposed by standing waves generated by the interference between the resist pattern and the incident wave, and stepped cuts occurred in the side surface portion of the resist pattern obtained after development.
  • the present inventors consider that it is effective to reduce the distance between the mask and the base material as much as possible in order to suppress the occurrence of the step-like cuts, and peel the temporary support to perform contact exposure. We thought it was preferable to do this. That is, the photosensitive transfer material according to the present disclosure is, for example, fine in that the contamination of the mask at the time of contact exposure is suppressed, and the occurrence of the stepped cut is suppressed by performing the contact exposure. It is also considered useful when forming a resist pattern.
  • the photosensitive transfer material according to the present disclosure will be described in detail.
  • FIG. 1 schematically illustrates an example of a layer configuration of a photosensitive transfer material according to the present disclosure.
  • a temporary support 10 In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 10, an intermediate layer 12, a positive photosensitive resin layer 14, and a cover film 16 are laminated in this order.
  • the intermediate layer 12 is in contact with the temporary support 10 and has an indentation hardness of 5.0 mN or more on the surface in contact with the temporary support.
  • the photosensitive transfer material according to the present disclosure is in contact with a temporary support, and an intermediate layer having an indentation hardness of 5.0 mN or more on the surface in contact with the temporary support is defined as a temporary support and a positive photosensitive resin layer.
  • middle layer is a layer used as the outermost layer in the photosensitive transfer material after peeling of a temporary support body.
  • the indentation hardness on the surface of the intermediate layer on the side in contact with the temporary support is 5.0 mN or more, preferably 5.2 mN or more, and more preferably 5.4 mN or more.
  • the upper limit of the indentation hardness of the intermediate layer is not particularly limited, but is preferably 50 mN or less. Within this range, problems such as cracks and delamination are unlikely to occur during lamination.
  • the indentation hardness is measured by the following measurement method. If necessary, the cover film is peeled off from the photosensitive transfer material, and the photosensitive transfer material is laminated on an alkali-cleaned glass plate (Corning EagleXG), and then the temporary support is peeled off from the boundary surface with the intermediate layer. Expose the layer. Under an environment of 25 ° C. and 60% RH (relative humidity), the surface of the exposed intermediate layer is subjected to a dynamic ultra-small hardness meter (DUH-W201 manufactured by Shimadzu Corporation) with a round indenter (Tokyo Diamond Tool Co., Ltd.). A model No.
  • the intermediate layer may be formed of any material as long as the indentation hardness is within the above range, but is preferably a layer that is removed by development.
  • the intermediate layer is preferably a water-soluble or water-dispersible layer from the viewpoint that it is preferably removed by development.
  • water-soluble means that the amount of the target substance dissolved in 100 parts by mass of water at 25 ° C. is 0.1 parts by mass or more.
  • water dispersibility means that the amount of precipitate after 24 hours is less than 0.01 parts by mass when 100 parts by mass of water at 25 ° C. and 0.1 parts by mass of the target substance are mixed.
  • the intermediate layer preferably contains a cellulose ether compound from the viewpoints of adhesion to the positive photosensitive resin layer, releasability from the temporary support, and the like.
  • the cellulose ether compound is a compound having a structure in which cellulose is etherified.
  • the cellulose ether compound is not particularly limited as long as the indentation hardness is 5.0 mN or more, and examples thereof include hydroxypropylmethylcellulose and hydroxypropylcellulose. Hydroxypropylmethylcellulose is preferable from the viewpoint of suppressing mask contamination.
  • the glass transition temperature (Tg) of the cellulose ether compound is preferably 100 ° C. to 200 ° C., more preferably 120 ° C. to 180 ° C.
  • the glass transition temperature can be measured using differential scanning calorimetry (DSC). The specific measurement method is performed in accordance with the method described in JIS K 7121 (1987) or JIS K 6240 (2011).
  • an extrapolated glass transition start temperature (hereinafter sometimes referred to as Tig) is used. The method for measuring the glass transition temperature will be described more specifically. When determining the glass transition temperature, hold at a temperature about 50 ° C.
  • 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 side baseline in the DTA curve or DSC curve to the high-temperature side, and the step-like 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
  • Tg As a method for adjusting Tg to the above-mentioned preferred range, for example, from the Tg of the homopolymer of each constituent unit of the target polymer and the mass ratio of each constituent unit, using the FOX formula as a guide, It is possible to control the Tg of the specific 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 constituent unit contained in the copolymer using the FOX formula described above. It is also possible to adjust the Tg of the polymer by adjusting the weight average molecular weight of the polymer.
  • the weight average molecular weight of the cellulose ether compound is preferably from 5,000 to 200,000, more preferably from 10,000 to 100,000, from the viewpoint of developability and the like.
  • cellulose ether compound Commercially available products may be used as the cellulose ether compound, and preferred commercial products are Metrose 60SH-03, Metrose 60SH-06, Metrose 60SH-15 (all manufactured by Shin-Etsu Chemical Co., Ltd.), NISSO HPC-SSL. HPC-SL, HPC-L (manufactured by Nippon Soda Co., Ltd.), CMC Daicel (manufactured by Daicel Finechem Co., Ltd.), HEC-AL-15 (manufactured by Sumitomo Seika Co., Ltd.), and the like.
  • Metrose 60SH-03 Metrose 60SH-06
  • Metrose 60SH-15 all manufactured by Shin-Etsu Chemical Co., Ltd.
  • NISSO HPC-SSL HPC-SL
  • HPC-L manufactured by Nippon Soda Co., Ltd.
  • CMC Daicel manufactured by Daicel Finechem Co., Ltd.
  • HEC-AL-15 manufactured by Sum
  • the intermediate layer in the present disclosure may contain one kind of cellulose ether compound or two or more kinds in combination.
  • the content of the cellulose ether compound is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and more preferably 25% by mass with respect to the total mass of the intermediate layer. % Or more is particularly preferable.
  • the upper limit of the content is not particularly limited and may be 100% by mass or less.
  • the intermediate layer in the present disclosure may further include particles from the viewpoint of improving the adhesion with the positive photosensitive resin layer or the second resin layer described later.
  • the particles include inorganic particles and resin particles. From the viewpoint of suppression of mask contamination, silica particles, alumina particles, or resin particles are preferable, silica particles or alumina particles are more preferable, and silica particles are preferable. More preferably it is.
  • Inorganic particles include inorganic oxide particles such as silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide, and the like. Can be mentioned.
  • the resin particles include homopolymers and copolymers of acrylic acid monomers such as acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, cellulose polymers such as nitrocellulose, methylcellulose, ethylcellulose, and cellulose acetate, Polyethylene, polypropylene, polystyrene, vinyl chloride copolymers, vinyl chloride-vinyl acetate copolymers, polyvinyl polymers such as polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl alcohol and copolymers of vinyl compounds, polyesters, polyurethanes, polyamides Condensation polymers such as butadiene-styrene copolymers, rubber thermoplastic polymers such as butadiene-styrene copolymers, polymers obtained by polymerizing and crosslinking photopolymerizable or thermopolymerizable compounds such as epoxy compounds, Emissions compounds and the like.
  • acrylic acid monomers such as acrylic
  • the surface of the 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 volume average particle diameter of the particles is preferably 10 nm to 200 nm.
  • the volume average particle diameter is measured using a particle size distribution measuring apparatus using light scattering (for example, Microtrack UPA (registered trademark) EX150 manufactured by Nikkiso Co., Ltd.).
  • the intermediate layer in the present disclosure may contain particles alone or in combination of two or more.
  • the volume fraction of the particles in the intermediate layer (the volume ratio occupied by the particles in the intermediate layer) is 5% by volume to 90% by volume 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% by volume to 80% by volume, more preferably 15% by volume to 70% by volume, and particularly preferably 20% by volume to 60% by volume.
  • the intermediate layer in the present disclosure may contain a known additive as required in addition to the cellulose ether compound.
  • additives other additives used for a positive photosensitive resin layer described later are preferably exemplified.
  • the intermediate layer may include two or more layers. From the viewpoint of production suitability, when the intermediate layer includes two or more layers, the intermediate layer preferably includes two layers.
  • the intermediate layer includes two or more layers, details of the layer in contact with the positive photosensitive resin layer included in the intermediate layer, the layer in contact with the temporary support included in the intermediate layer, and other layers Will be described.
  • the layer in contact with the positive photosensitive resin layer preferably contains a cellulose ether compound.
  • the shape of the resist pattern obtained after development is unlikely to change even when time elapses after exposure.
  • excellent placement stability PED (post exposure delay)
  • leaving the photosensitive transfer material for a certain period of time after exposure and before development is called “placing after exposure”.
  • Hydroxypropyl cellulose or hydroxypropyl methylcellulose is preferable and hydroxypropylcellulose is more preferable.
  • the weight average molecular weight of the cellulose ether compound is preferably from 5,000 to 200,000, more preferably from 10,000 to 100,000, from the viewpoint of developability and the like.
  • HPC-SSL manufactured by Nippon Soda Co., Ltd.
  • Metrolze 60SH-03 Metrolze 60SH-06
  • Metrolze 60SH-15 all Shin-Etsu Chemical Co., Ltd.
  • the lower layer may contain one kind of cellulose ether compound or two or more kinds in combination.
  • the content of the cellulose ether compound is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and 25% by mass with respect to the total mass of the lower layer.
  • the above is particularly preferable.
  • the upper limit of the content is not particularly limited and may be 100% by mass or less.
  • the indentation hardness on the surface in contact with the temporary support of the layer in contact with the temporary support in the intermediate layer is 5.0 mN or more.
  • the layer in contact with the temporary support in the intermediate layer is also referred to as “upper layer”.
  • the preferred embodiment of the layer in contact with the temporary support in the intermediate layer is the same as the preferred embodiment of the intermediate layer described above.
  • the layer in contact with the temporary support in the intermediate layer contains hydroxypropylmethylcellulose
  • the layer in contact with the positive photosensitive resin layer in the intermediate layer contains hydroxypropylcellulose. It is preferable.
  • the intermediate layer includes three or more layers, other layers are included between the upper layer and the lower layer.
  • the layer containing a cellulose ether compound is mentioned.
  • the cellulose ether compound contained in the above-mentioned upper layer or lower layer is mentioned.
  • the thickness of the intermediate layer (when the intermediate layer includes two or more layers, the total thickness of all the layers included in the intermediate layer) is 0.1 ⁇ m to 10 ⁇ m from the viewpoint of further improving the effect of contact exposure.
  • 0.2 ⁇ m to 8 ⁇ m is more preferable, and 0.5 ⁇ m to 5 ⁇ m is particularly preferable.
  • middle layer is thinner than the thickness of the positive photosensitive resin layer mentioned later.
  • the thickness of the upper layer is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.2 ⁇ m to 8 ⁇ m, and more preferably 0.5 ⁇ m to 5 ⁇ m from the viewpoint of further improving the effect of contact exposure. Is particularly preferred.
  • the thickness of the lower layer is preferably from 0.1 ⁇ m to 10 ⁇ m, more preferably from 0.2 ⁇ m to 8 ⁇ m, from the viewpoint of further improving the stability of the holding and the effect of contact exposure. 0.5 ⁇ m to 5 ⁇ m is particularly preferable.
  • the method for forming the intermediate layer is not particularly limited, and for example, the intermediate layer can be formed by using a composition for forming an intermediate layer. Specifically, each component contained in the intermediate layer and the solvent are mixed at a predetermined ratio and in an arbitrary method, and dissolved by stirring to prepare an intermediate layer forming composition for forming the intermediate layer. Can do. For example, it is possible to prepare a composition by preparing each solution of each component in advance in a solvent and then mixing the obtained solution at a predetermined ratio. The composition prepared as described above can be used after being filtered using a filter having a pore size of 5 ⁇ m.
  • 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 photosensitive resin composition mentioned later may be apply
  • the coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
  • the intermediate layer includes two or more layers, it can be formed by sequentially applying a plurality of intermediate layer forming compositions.
  • the temporary support is a support that supports the intermediate layer and the positive photosensitive resin layer and is peelable from the intermediate layer.
  • 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.
  • 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 temporary support may have a layer that is peeled off together with the temporary support when the temporary support is peeled off.
  • the thickness of the temporary support is not particularly limited, but is preferably in the range of 1 ⁇ m to 200 ⁇ m, and more preferably in the range of 5 ⁇ m to 100 ⁇ m from the viewpoint of ease of handling and versatility.
  • the thickness of the temporary support is selected according to the material from the viewpoints of strength as a support, flexibility required for bonding to a circuit wiring forming substrate, light transmittance required in the first exposure process, etc. do it.
  • the photosensitive transfer material according to the present disclosure has a positive photosensitive resin layer.
  • the positive photosensitive resin layer preferably contains a polymer having a structural unit having an acid group protected with an acid-decomposable group, and a photoacid generator.
  • the positive photosensitive resin layer in the present disclosure is preferably a chemically amplified positive photosensitive resin layer.
  • the photoacid generators such as onium salts and oxime sulfonate compounds described below are produced in response to active energy rays (active rays), and the deprotection of the protected acid groups in the specific polymer.
  • the acid generated by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as the power of 10, which is a so-called chemical High sensitivity is obtained as a result of amplification.
  • a quinonediazide compound is used as a photoacid generator sensitive to active energy rays, a carboxy group is generated by a sequential photochemical reaction, but its quantum yield is always 1 or less and does not correspond to a chemical amplification type. .
  • the positive photosensitive resin layer includes a polymer (also referred to as “specific polymer”) having a structural unit (also referred to as “structural unit A”) having an acid group protected with an acid-decomposable group. Is preferred.
  • the positive photosensitive resin layer may contain other polymers in addition to the polymer having the structural unit A.
  • the polymer having the structural unit A and other polymers are also collectively referred to as “polymer component”.
  • the structural unit A having an acid-decomposable protected acid group in the specific polymer undergoes a deprotection reaction to be an acid group by the action of a catalytic amount of an acidic substance generated by exposure. This acid group enables a curing reaction.
  • the positive photosensitive resin layer may further contain a polymer other than the polymer having a structural unit having an acid group protected by acid decomposability. Moreover, it is preferable that all the polymers contained in the said polymer component are polymers which have at least the structural unit which has the acid group mentioned later, respectively.
  • the chemically amplified positive photosensitive resin composition may further contain a polymer other than these.
  • the polymer component in the present disclosure means a material including other polymers added as necessary. In addition, even if it is a high molecular compound, the compound applicable to surfactant, a crosslinking agent, and a dispersing agent mentioned later shall not be contained in the said polymer component.
  • the specific polymer is preferably an addition polymerization type resin, and more preferably a polymer having a structural unit derived from (meth) acrylic acid or an ester thereof.
  • the positive photosensitive resin layer includes, as a specific polymer, a structural unit represented by any one of the above formulas A1 to A3 as a specific polymer from the viewpoint of solubility in a developer, transferability, and the like. It is preferable that a polymer (hereinafter, also referred to as “polymer A-1”) is included.
  • a polymer hereinafter, also referred to as “polymer A-1”
  • the specific polymer as the structural unit A, a structural unit represented by any one of the above formulas A1 to A3, and It is more preferable to include a polymer having an acid group.
  • the specific polymer contained in the positive photosensitive resin layer may be one type or two or more types.
  • the polymer component preferably includes a polymer A-1 having at least a structural unit A having an acid group protected with an acid-decomposable group.
  • the polymer component contains a polymer having the structural unit A, an extremely sensitive chemical amplification positive type positive photosensitive resin layer can be obtained.
  • the “acid group protected with an acid-decomposable group” in the present disclosure those known as an acid group and an acid-decomposable group can be used, and are not particularly limited.
  • Specific examples of the acid group preferably include a carboxy group and a phenolic hydroxyl group.
  • the acid group protected by acid decomposability is a group that is relatively easily decomposed by an acid (for example, an ester group, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group protected by a group represented by the formula A3).
  • An acetal functional group such as tert-butyl ester group or a tertiary alkyl carbonate group such as tert-butyl carbonate group or the like. it can.
  • the acid-decomposable group is preferably a group having a structure protected in the form of an acetal.
  • the acid-decomposable group is preferably an acid-decomposable group having a molecular weight of 300 or less from the viewpoint of suppressing variation in line width in the obtained circuit wiring.
  • the structural unit A having an acid group protected with an acid-decomposable group preferably contains a structural unit represented by any one of the following formulas A1 to A3 from the viewpoint of sensitivity and resolution. More preferably, it includes a structural unit represented by -2.
  • R 11 and R 12 each independently represents a hydrogen atom, an alkyl group or an aryl group, at least one of R 11 and R 12 is an alkyl group or an aryl group, and R 13 is an alkyl group or Represents an aryl group, R 11 or R 12 and R 13 may be linked to form a cyclic ether, R 14 represents a hydrogen atom or a methyl group, and X 1 represents a single bond or a divalent linking group.
  • R 15 represents a substituent, and n represents an integer of 0 to 4.
  • R 21 and R 22 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 21 and R 22 is an alkyl group or an aryl group, and R 23 is an alkyl group or Represents an aryl group, and R 21 or R 22 and R 23 may combine to form a cyclic ether, and each R 24 independently represents a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, Represents an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.
  • 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, 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, X 0 represents a single bond or an arylene group, Y represents —S— or —O—.
  • R 11 or R 12 when R 11 or R 12 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R 11 or R 12 is an aryl group, a phenyl group is preferable. R 11 and R 12 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 13 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 11 to R 13 may have a substituent.
  • R 11 or R 12 and R 13 may be linked to form a cyclic ether, and R 11 or R 12 and R 13 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 1 represents a single bond or a divalent linking group, and is 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 15 represents a substituent, 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 14 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the Tg of the polymer A-1 can be further lowered. More specifically, the structural unit in which R 14 in Formula A1 is a hydrogen atom is preferably 20% by mass or more based on the total content of the structural unit A contained in the polymer A-1. In addition, the content (content ratio: mass ratio) of the structural unit in which R 14 in formula A1 is a hydrogen atom in the structural unit A is calculated by a conventional method from 13 C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of the peak intensity.
  • NMR 13 C-nuclear magnetic resonance spectrum
  • the structural unit represented by the following formula A1-2 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 Represents an integer of 0-4.
  • R B4 is preferably a hydrogen atom.
  • R B5 to R B11 are preferably hydrogen atoms.
  • Formulas A1-2 and R B12 represent a substituent, and are 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.
  • R 21 and R 22 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferable.
  • R 21 and R 22 are aryl groups, a phenyl group is preferable.
  • R 11 and R 12 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably at least one is a hydrogen atom.
  • R 23 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
  • R 11 or R 12 and R 13 may be linked to form a cyclic ether.
  • each R 24 is preferably independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. R 24 may be further substituted with the same group as R 24 .
  • m is preferably 1 or 2, and more preferably 1.
  • R 31 or R 32 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable.
  • 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.
  • Y represents —S— or —O—, and —O— is preferable from the viewpoint of exposure sensitivity.
  • the structural unit represented by the formula A3 is a structural unit having a carboxy group protected with an acid-decomposable group.
  • the polymer A-1 contains the structural unit represented by the formula A3, the sensitivity at the time of pattern formation is excellent, and the resolution is excellent.
  • 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-1 can be further lowered. More specifically, the structural unit in which R 34 in formula A3 is a hydrogen atom is preferably 20% by mass or more based on the total amount of the structural unit represented by formula A3 contained in polymer A-1.
  • the content (content ratio: mass ratio) of the structural unit in which R 34 in the formula A1 is a hydrogen atom is usually determined from 13 C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of the peak intensity calculated by the method.
  • the structural unit represented by the following formula A3-2 is more preferable from the viewpoint of further increasing the exposure sensitivity during pattern formation.
  • 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 R 31 or R 32 and R 33 may be linked to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or an arylene group.
  • R 31, R 32, R 33 , R 34 and X 0 has the same meaning as R 31, R 32, R 33 , R 34 and X 0 in formula A3, preferred embodiments as well It is.
  • the structural unit represented by the following formula A3-3 is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.
  • R 34 represents a hydrogen atom or a methyl group
  • R 35 to R 41 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 34 is preferably a hydrogen atom.
  • R 35 to R 41 are preferably hydrogen atoms.
  • R 34 represents a hydrogen atom or a methyl group.
  • the structural unit A contained in the polymer A-1 may be one type or two or more types.
  • the content of the structural unit A in the polymer A-1 is preferably 20% by mass or more, more preferably 20% by mass to 90% by mass with respect to the total mass of the polymer A-1. More preferably, it is 30% by mass to 70% by mass.
  • the content (content ratio: mass ratio) of the structural unit A in the polymer A-1 can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from 13 C-NMR measurement.
  • the proportion of the structural unit A is preferably 5% by mass to 80% by mass with respect to the total mass of the polymer component, It is more preferably 10% by mass to 80% by mass, and particularly preferably 30% by mass to 70% by mass.
  • the polymer A-1 preferably contains a structural unit B having an acid group.
  • the structural unit B is a structural unit having a protective group, for example, an acid group that is not protected by an acid-decomposable group, that is, an acid group that does not have a protective group.
  • the acid group in this specification means a proton dissociable group having a pKa of 12 or less.
  • the acid group is usually incorporated into a polymer as a structural unit having an acid group (structural unit B) using a monomer capable of forming an acid group.
  • structural unit B structural unit having 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 examples 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 carboxylic acid group and a phenolic hydroxyl group is preferable.
  • Introduction of the structural unit having an acid group into the polymer A-1 is carried out by copolymerizing a monomer having an acid group or by copolymerizing a monomer having an acid anhydride structure and hydrolyzing the acid anhydride. Can do.
  • the structural unit having an acid group which is the structural unit B, is derived from a structural unit derived from a styrene compound or a structural unit obtained by substituting an acid group for a structural unit derived from a vinyl compound, or (meth) acrylic acid. More preferred is a structural unit.
  • the monomer having a carboxy group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene, and the like. Examples thereof include hydroxystyrene and 4-hydroxyphenyl methacrylate, and examples of the monomer having an acid anhydride include maleic anhydride.
  • a structural unit having a carboxylic acid group or a structural unit having a phenolic hydroxyl group is preferable from the viewpoint that the sensitivity at the time of pattern formation becomes better.
  • the monomer having an acid group that can form the structural unit B is not limited to the examples described above.
  • the structural unit B contained in the polymer A-1 may be only one type or two or more types.
  • the polymer A-1 preferably contains 0.1% by mass to 20% by mass of a structural unit having an acid group (structural unit B) with respect to the total mass of the polymer A-1.
  • the content is more preferably 15% by mass, and further preferably 1% by mass to 10% by mass. When it is in the above range, the pattern formability becomes better.
  • the content (content ratio: mass ratio) of the structural unit B in the polymer A-1 can be confirmed by the intensity ratio of the peak intensity calculated by a conventional method from 13 C-NMR measurement.
  • styrenes (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester , Bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic anhydrides, groups having an aliphatic cyclic skeleton, Mention may be made of saturated compounds.
  • the Tg of the polymer A-1 can be easily adjusted.
  • the glass transition temperature By setting the glass transition temperature to 120 ° C. or less, the positive photosensitive resin layer containing the polymer A-1 can maintain a good level of transferability and peelability from the temporary support while forming a pattern. Better resolution and sensitivity.
  • the polymer A-1 may contain only one type of structural unit C, or may contain two or more types of structural unit C.
  • the structural unit C specifically includes styrene, tert-butoxystyrene, methylstyrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, (meth) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) Mention may be made of structural units formed by polymerizing benzyl acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate, or the like. In addition, the compounds described in paragraphs 0021 to
  • the structural unit C a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton is preferable from the viewpoint of improving the electrical characteristics of the obtained transfer material.
  • 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 C is preferably a structural unit derived from cyclohexyl (meth) acrylate.
  • (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion.
  • (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion.
  • Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • the content of the structural unit C 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-1.
  • 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 polymer A-1 also contains a structural unit having an ester of an acid group in the structural unit B as the structural unit C. This also optimizes the solubility in the developer and the physical properties of the positive photosensitive resin layer. It is preferable from a viewpoint of making it.
  • the polymer A-1 preferably includes a structural unit having a carboxylic acid group as the structural unit B, and further includes a structural unit C including a carboxylic acid ester group as a copolymerization component.
  • a polymer containing the structural unit B derived from acrylic acid and the structural unit (c) derived from cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate is more preferred.
  • preferred examples of the polymer A-1 in the present disclosure will be given, but the present disclosure is not limited to the following examples.
  • the ratio of the structural unit and the weight average molecular weight in the following exemplary compounds are appropriately selected in order to obtain preferable physical properties.
  • the glass transition temperature (Tg) of the polymer A-1 in the present disclosure is preferably 90 ° C. or less, and preferably 20 ° C. or more and 60 ° C. from the viewpoint of transferability and the adjustment of the heating temperature in the heating step described above. More preferably, the temperature is not higher than 30 ° C, and more preferably not lower than 30 ° C and not higher than 50 ° C.
  • the Tg of the polymer As a method for adjusting the Tg of the polymer to the above-described preferable range, for example, from the Tg of the homopolymer of each constituent unit of the target polymer and the mass ratio of each constituent unit, using the FOX formula as a guideline It is possible to control the Tg of the target polymer A-1.
  • 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 constituent unit contained in the copolymer using the FOX formula described above. It is also possible to adjust the Tg of the polymer by adjusting the weight average molecular weight of the polymer.
  • the acid value of the polymer A-1 is preferably 0 mgKOH / g or more and 200 mgKOH / g or less, and more preferably 5 mgKOH / g or more and 100 mgKOH / g or less, from the viewpoints of developability and transferability.
  • A 56.11 ⁇ Vs ⁇ 0.1 ⁇ f / w
  • Vs Amount of 0.1 mol / l sodium hydroxide aqueous solution required for titration (mL)
  • f Potency of 0.1 mol / l sodium hydroxide aqueous solution
  • the molecular weight of the polymer A-1 is preferably 60,000 or less in terms of polystyrene-equivalent weight average molecular weight.
  • the melt viscosity of the positive photosensitive resin layer is suppressed to be low, and bonding at a low temperature (for example, 130 ° C. or less) is performed when bonding to the substrate.
  • the weight average molecular weight of the polymer A-1 is preferably 2,000 to 60,000, and more preferably 3,000 to 50,000.
  • the ratio (dispersity) between the number average molecular weight and the weight average molecular weight of the polymer A-1 is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.
  • the production method (synthesis method) of the polymer A-1 is not particularly limited.
  • a polymerizable monomer for forming the structural unit A represented by the formula A, and a structural unit B having an acid group It is synthesized by polymerizing using a polymerization initiator in an organic solvent containing a polymerizable monomer for forming a polymer and, if necessary, a polymerizable monomer for forming other structural unit C. be able to. It can also be synthesized by a so-called polymer reaction.
  • the positive photosensitive resin layer is 50% by mass to 99% by mass of the polymer component with respect to the total solid content of the positive photosensitive resin layer from the viewpoint of developing good adhesion to the substrate. It is preferably included in a proportion of .9% by mass, more preferably in a proportion of 70% by mass to 98% by mass.
  • the positive photosensitive resin layer has a content of 50% by mass or more of the polymer A-1 with respect to the total solid content of the positive photosensitive resin layer from the viewpoint of developing good adhesion to the substrate. It is preferably contained in a proportion of 99.9% by mass, more preferably in a proportion of 70% by mass to 98% by mass.
  • the positive photosensitive resin layer includes, as a polymer component, the structural unit (a) represented by the formula A as long as the effects of the photosensitive transfer material according to the present disclosure are not impaired in addition to the polymer A-1.
  • the polymer may further be included (sometimes referred to as “other polymer”).
  • the blending amount of the other polymer is preferably 50% by mass or less and more preferably 30% by mass or less in the total polymer component. Preferably, it is 20 mass% or less.
  • the positive photosensitive resin layer may contain only one type of other polymer or two or more types.
  • polyhydroxystyrene can be used, which are commercially available, such as SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer).
  • ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 above, manufactured by Toagosei Co., Ltd.
  • Joncryl 690, Joncryl 6 Joncryl 67, Joncryl 586 manufactured by BASF or the like can also be used.
  • the positive photosensitive resin layer preferably contains a photoacid generator.
  • the photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiation with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
  • the photoacid generator used in the present disclosure is preferably a compound that generates an acid in response to an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but its chemical structure is not limited.
  • a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
  • the 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.
  • 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.
  • a aryl group for R 21 an aryl group having 6 to 18 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable.
  • the aryl group of R 21 may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a halogen atom.
  • the compound having an oxime sulfonate structure represented by the formula (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 positive photosensitive resin layer is 0.1% by mass to 10% by mass with respect to the total mass of the positive photosensitive resin layer from the viewpoint of sensitivity and resolution. And more preferably 0.5 to 5% by mass.
  • the positive photosensitive resin layer may contain a solvent.
  • the photosensitive resin composition for forming the positive photosensitive resin layer is for easily forming the positive photosensitive resin layer.
  • the positive photosensitive resin layer can be suitably formed by applying and drying a photosensitive resin composition containing a solvent.
  • 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 JP2011-221494A, 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. 900 parts by mass is more preferable. Further, the content of the solvent in the positive photosensitive resin layer is preferably 2% by mass or less, more preferably 1% by mass or less, based on the total mass of the positive photosensitive resin layer. More preferably, it is 0.5 mass% or less.
  • the positive photosensitive resin layer in the present disclosure may contain a known additive as required in addition to the polymer A-1 and the photoacid generator.
  • the positive 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-1.
  • 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-1 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
  • compound X is a chemically amplified positive type obtained by mixing compound X, polymer A-1 and a photoacid generator. If the photosensitive resin composition does not improve the plasticity as compared to the chemically amplified positive photosensitive resin composition formed without the compound X, it 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 preferably 2% by mass to 20% by mass with respect to the total mass of the positive photosensitive resin layer from the viewpoint of adhesion. Is more preferable.
  • the positive photosensitive resin layer may contain only one kind of plasticizer or may contain two or more kinds.
  • the positive photosensitive resin layer may 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 positive photosensitive resin layer. .
  • the positive photosensitive resin layer preferably further contains a basic compound.
  • the basic compound can be arbitrarily selected from basic compounds used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include compounds described in JP-A-2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
  • 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, 1,5-diazabicyclo [4.3.0] -5-nonene, and 1,8-diazabicyclo [5.3.0] -7-Undecene.
  • Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
  • Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
  • the said basic compound may be used individually by 1 type, or may use 2 or more types together.
  • the content of the basic compound is preferably 0.001% by mass to 5% by mass and more preferably 0.005% by mass to 3% by mass with respect to the total mass of the positive photosensitive resin layer. More preferred.
  • the positive photosensitive resin layer in the present disclosure can include a heterocyclic compound.
  • a heterocyclic compound There is no restriction
  • a heterocyclic monomer having silicon, sulfur, phosphorus or the like can be added.
  • the addition amount of the heterocyclic compound in the positive photosensitive resin layer is 0.01% by mass to 50% by mass with respect to the total mass of the positive photosensitive resin layer when the heterocyclic compound is added. It is preferably 0.1% by mass to 10% by mass, more preferably 1% by mass to 5% by mass. It is preferable in the said range from a viewpoint of adhesiveness and etching tolerance. Only 1 type may be used for a heterocyclic compound and it can also use 2 or more types together.
  • Specific examples of the compound having an epoxy group in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like.
  • a compound having an epoxy group in the molecule can be obtained as a commercial product.
  • JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Co., Ltd.), JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like, such as commercial products described in paragraph 0189 of JP2011-221494A can be mentioned.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and aliphatic epoxy resin is particularly preferable.
  • the compound containing an oxetanyl group is preferably used alone or mixed with a compound containing an epoxy group.
  • the heterocyclic compound is preferably a compound having an epoxy group from the viewpoint of etching resistance and line width stability.
  • the positive 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 positive photosensitive resin layer preferably contains a surfactant from the viewpoint of film thickness uniformity.
  • a surfactant any of anionic, cationic, nonionic (nonionic), or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. .
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • F-Top manufactured by JEMCO
  • MegaFac registered trademark
  • Fluorard manufactured by Sumitomo 3M
  • Asahi Guard Asahi Guard
  • Surflon registered trademark
  • PolyFox manufactured by OMNOVA
  • SH-8400 manufactured by Toray Dow Corning Co., Ltd.
  • a surfactant it contains a structural unit A and a structural unit B represented by the following formula I-1, and is a weight average in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
  • a preferable example is a copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less.
  • R 401 and R 403 each independently represent a hydrogen atom or a methyl group
  • R 402 represents a linear alkylene group having 1 to 4 carbon atoms
  • R 404 represents a hydrogen atom or a carbon group.
  • L represents an alkylene group having 3 to 6 carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p is a numerical value of 10 mass% to 80 mass%.
  • Q represents a numerical value of 20% to 90% by mass
  • r represents an integer of 1 to 18
  • s represents an integer of 1 to 10
  • * represents a bonding site with another structure.
  • L is preferably a branched alkylene group represented by the following formula (I-2).
  • R 405 in formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred.
  • the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
  • Surfactant may be used individually by 1 type and may use 2 or more types together.
  • the addition amount of the surfactant is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass with respect to the total mass of the positive photosensitive resin layer. More preferably, the content is 01% by mass to 3% by mass.
  • the positive photosensitive resin layer in the present disclosure includes metal oxide particles, an antioxidant, a dispersant, an acid multiplier, a development accelerator, a conductive fiber, a colorant, a thermal radical polymerization initiator, a thermal acid generator, Known additives such as ultraviolet absorbers, thickeners, crosslinking agents, and organic or inorganic suspending agents can be further added. Preferred embodiments of the other components are described in paragraphs 0165 to 0184 of JP-A-2014-85643, respectively, and the contents of this publication are incorporated in this specification.
  • a photosensitive resin composition for forming a positive photosensitive resin layer can be prepared by mixing each component and a solvent in an arbitrary ratio and by an arbitrary method, and stirring and dissolving. For example, it is possible to prepare a composition by preparing each solution of each component in advance in a solvent and then mixing the obtained solution at a predetermined ratio.
  • the composition prepared as described above can be used after being filtered using a filter having a pore size of 0.2 ⁇ m or the like.
  • a positive photosensitive resin layer can be formed by applying the photosensitive resin composition onto the above-mentioned intermediate layer forming composition and drying it as necessary. Moreover, you may apply
  • the coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
  • a positive photosensitive resin layer can be applied after forming other layers described later on the intermediate layer.
  • the photosensitive transfer material according to the present disclosure may have a layer other than the positive photosensitive resin layer (hereinafter also referred to as “other layer”).
  • other layers include a contrast enhancement layer, a cover film, a layer containing a known ultraviolet absorber, a thermoplastic resin layer, and an adhesion layer.
  • the photosensitive transfer material according to the present disclosure may have a cover film.
  • the cover film include a resin film and paper.
  • a resin film is particularly preferable from the viewpoint of strength and flexibility.
  • the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a polyethylene terephthalate film is preferable, and a biaxially stretched polyethylene terephthalate film is particularly preferable.
  • the thickness of the cover film is not particularly limited, and for example, a thickness of 1 ⁇ m to 2 mm is preferable.
  • the photosensitive transfer material according to the present disclosure preferably further includes a thermoplastic resin layer between the temporary support and the intermediate layer from the viewpoint of transferability.
  • the thermoplastic resin layer is preferably peeled between the intermediate layer and the thermoplastic resin layer when the temporary support is peeled off. That is, it is preferable that the thermoplastic resin layer is peeled off together with the temporary support.
  • 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 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 thermoplastic organic polymer and an additive are dissolved on a temporary support.
  • 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 resin composition prepared using a solvent that does not dissolve the intermediate layer is further applied, and dried to laminate a positive photosensitive resin layer, whereby the photosensitive property according to the present disclosure is obtained.
  • a transfer material can be suitably produced.
  • the photosensitive transfer material according to the present disclosure can have a contrast enhancement layer in addition to the positive photosensitive resin layer. It is preferable to have a contrast enhancement layer between the intermediate layer and the positive photosensitive resin layer.
  • 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).
  • Known 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 photosensitive transfer material according to the present disclosure may have a layer containing an ultraviolet absorber (ultraviolet absorbing layer).
  • the ultraviolet absorbing layer is preferably included on the opposite side of the positive photosensitive resin layer from the intermediate layer.
  • the aspect which has a ultraviolet absorption layer between a cover film and a positive photosensitive resin layer is mentioned.
  • an ultraviolet absorbing layer is present between the substrate and the positive photosensitive resin layer. According to such an aspect, it is considered that the reflection of the exposure light by the base material is reduced, and the influence of the exposure by the standing wave generated by the interference between the reflected wave and the incident wave is reduced.
  • ultraviolet absorber known ultraviolet absorbers can be used without any particular limitation. Salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel-chelate-based, hindered amine-based compounds, and polymers containing these structures Or inorganic ultraviolet absorbers, such as a metal oxide, etc. are mentioned.
  • the photosensitive transfer material according to the present disclosure may further have an adhesion layer between the cover film and the positive photosensitive resin layer as another layer.
  • an adhesion layer By having the adhesion layer, the adhesion when transferred to a substrate or the like is improved.
  • the method for producing a resist pattern according to the present disclosure is not particularly limited, Bonding the temporary support of the photosensitive transfer material according to the present disclosure to the substrate while bringing the outermost layer on the positive photosensitive resin layer side into contact with the substrate; and Peeling the temporary support of the photosensitive transfer material; A step of pattern exposure of the positive photosensitive resin layer by bringing a photomask into contact with the photosensitive transfer material from which the temporary support has been peeled; It is preferable that the positive photosensitive resin layer after the exposing step is developed to form a resist pattern in this order.
  • the circuit wiring manufacturing method according to the present disclosure includes the photosensitive layer according to the present disclosure.
  • the “outermost layer on the positive photosensitive resin layer side” in the photosensitive transfer material is the present disclosure having a temporary support, an intermediate layer, and a positive photosensitive resin layer in this order.
  • it means not the outermost layer on the temporary support side but the outermost layer on the positive photosensitive resin layer side.
  • the “outermost layer on the positive photosensitive resin layer side” is the outermost layer on the positive photosensitive resin layer side after the cover film is peeled off when the photosensitive transfer material has a cover film.
  • the support is also referred to as a “base material”, and the support having a conductive layer on the surface is also referred to as a “substrate”.
  • photosensitive resin layers 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 present disclosure uses the positive photosensitive resin layer.
  • an embodiment in which exposure is performed twice or more is also preferable.
  • the method of manufacturing a resist pattern according to the present disclosure or the method of manufacturing a circuit wiring according to the present disclosure includes a step of attaching the temporary support of the photosensitive transfer material according to the present disclosure to the positive photosensitive resin layer side with respect to a substrate. It is preferable to include a step of bonding the outermost layer in contact with the substrate (bonding step).
  • bonding step When the photosensitive transfer material which concerns on this indication has the said cover film, in the bonding process, bonding is performed after peeling a cover film.
  • the substrate and the photosensitive transfer material from which the cover film has been peeled off as necessary are pressure-bonded so that the substrate and the outermost layer on the positive photosensitive resin layer side are in contact with each other. It is preferable to do.
  • the positive type photosensitive resin layer by which the pattern formation after exposure and image development can be used suitably as an etching resist at the time of etching a conductive layer.
  • a well-known transfer method and a lamination method can be used. Specifically, the substrate and the photosensitive transfer material are overlapped so that the outermost layer on the positive photosensitive resin layer side of the photosensitive transfer material and the conductive layer are in contact with each other, and pressure is applied by a roll or the like. And the method performed to heating is mentioned preferably.
  • a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase the productivity can be used.
  • the pressure and temperature of the bonding in the bonding step and the surface material of the support to be bonded, for example, the material of the conductive layer and the positive photosensitive resin layer, the conveyance speed, and the pressure bonding machine used, etc. Can be set as appropriate. Further, in the case where the cover film is provided on the positive photosensitive resin layer of the photosensitive transfer material, the cover film may be removed from the positive photosensitive resin layer and then bonded. When the base material is a resin film, a roll-to-roll pressure bonding may be performed.
  • a support body is a glass base material 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 with low optical distortion and a substrate with high transparency.
  • Specific materials include polyethylene terephthalate (PET), Examples thereof include polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.
  • Examples of the conductive layer formed on the support include any conductive layer used for general wiring or touch panel wiring. It is also preferable that a plurality of conductive layers are formed on the support.
  • 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 for a visual recognition part used in a capacitive touch panel or a wiring for a peripheral extraction part.
  • the substrate (wiring forming substrate) used in the present disclosure is preferably a substrate having a conductive layer on the surface of the base material.
  • a wiring is formed by patterning the conductive layer.
  • a film substrate such as PET is preferably provided with a plurality of conductive layers such as metal oxides and metals.
  • the resist pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure preferably includes a step of peeling the temporary support of the photosensitive transfer material (temporary support peeling step).
  • temporary support peeling step There is no restriction
  • the positive photosensitive resin layer is formed by bringing a photomask into contact with the photosensitive transfer material from which the temporary support has been removed. It is preferable to include a pattern exposure step (exposure step). In the exposure process, the exposure mask contacts the intermediate layer. By performing exposure with the exposure mask and the intermediate layer in contact with each other, there is an advantage that the distance between the positive photosensitive resin layer and the mask is reduced, so that the resolution of the pattern is improved.
  • the exposure step it is preferable to irradiate the base material on which at least the intermediate layer and the positive photosensitive resin layer are formed with actinic rays through a mask having a pattern.
  • the photoacid generator contained in the positive photosensitive resin layer is decomposed to generate an acid, and the acid-decomposable group contained in the coating film component is hydrolyzed by the catalytic action of the generated acid.
  • an acid group such as a carboxy group or a phenolic hydroxyl group is formed.
  • the detailed arrangement and specific size of the pattern in the mask are not particularly limited.
  • 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.
  • 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, g-line (436 nm), i-line (365 nm) 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.
  • various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
  • Exposure dose depending on the positive photosensitive resin layer to be used may be appropriately selected, but is preferably from 5mJ / cm 2 ⁇ 200mJ / cm 2, it is 10mJ / cm 2 ⁇ 100mJ / cm 2 More preferred. It is also preferable to perform heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure. By a process called PEB (Post Exposure Bake), it is possible to reduce pattern edge roughness due to standing waves generated in the positive photosensitive resin layer during exposure.
  • PEB Post Exposure Bake
  • the resist pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure preferably includes a step of developing the positive photosensitive resin layer to form a resist pattern (developing step).
  • the exposed part in the positive photosensitive resin layer is removed by the development process.
  • Development of the exposed positive photosensitive resin layer in the development step can be performed using a developer.
  • the developer is not particularly limited as long as the positive photosensitive resin layer can be developed.
  • a known developer such as a developer described in JP-A No. 5-72724 can be used.
  • the developer is preferably a developer in which the portion where the positive photosensitive resin layer is removed 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 a developer onto the positive photosensitive resin layer after exposure. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
  • the liquid temperature of the developer is preferably 20 ° C. to 40 ° C.
  • the method for producing a resist pattern according to the present disclosure includes a step of washing with water after development, a step of drying a support having the obtained resist pattern, and the like. A known process may be included.
  • the post-baking process which heat-processes the resist pattern obtained by image development.
  • the post-baking is preferably performed in an environment of 8.1 kPa or more, and more preferably in an environment of 50.66 kPa or more. On the other hand, it is preferably performed in an environment of 121.6 kPa or less, more preferably in an environment of 111.46 kPa or less, and particularly preferably in an environment of 101.3 kPa or less.
  • the post-baking temperature is preferably 80 ° C. to 250 ° C., more preferably 110 ° C. to 170 ° C., and particularly preferably 130 ° C. to 150 ° C.
  • the post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
  • the post-bake may be performed in an air environment or a nitrogen substitution environment.
  • the transport speed of the support in each step in the method for producing a resist pattern according to the present disclosure or the method for producing a circuit wiring according to the present disclosure is not particularly limited, but is 0.5 m / It is preferably from min to 10 m / min, and more preferably from 2.0 m / min to 8.0 m / min except during exposure.
  • the circuit wiring manufacturing method preferably includes a step (etching step) of etching the substrate in a region where the resist pattern is not disposed.
  • the conductive layer is etched using the pattern formed from the positive 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 support having the etched conductive layer (cleaning process) and a support having the etched conductive layer as necessary.
  • You may perform the process (drying process) of drying a body.
  • the substrate may be cleaned with pure water for 10 seconds to 300 seconds at room temperature (10 ° C. to 35 ° C.).
  • air blow may be used, and the air blow pressure (preferably about 0.1 kg / cm 2 to 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 resist pattern using peeling liquid after the said etching process.
  • the patterned positive photosensitive resin layer remains. If the positive photosensitive resin layer is unnecessary, all the remaining positive photosensitive resin layers may be removed.
  • the above-mentioned positive photosensitive resin layer (resist pattern) or the like is preferably applied to the stripping solution being stirred at 30 to 80 ° C., more preferably 50 to 80 ° C. Examples thereof include a method of immersing the base material having 5 to 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 resist 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 method for manufacturing a circuit wiring according to the present disclosure may include a step of reducing the visible light reflectance of the surface of the conductive layer, for example, a part or all of the surface of the conductive layer on the support.
  • 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 for manufacturing a circuit wiring according to the present disclosure includes a step of forming an insulating film on a support having the conductive layer, for example, a formed wiring (the etched conductive layer), and a new method on the insulating film. Including a step of forming a conductive layer.
  • a conductive layer There is no restriction
  • 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. Good.
  • the wiring board 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 support has a plurality of conductive layers on both surfaces, and the circuit is sequentially or simultaneously applied to the conductive layers formed on both surfaces of the support. It is also preferable to form.
  • the first conductive pattern (first wiring) is formed on one surface of the support, and the second conductive pattern (second wiring) is formed on the other surface, preferably for a touch panel Wiring can be formed.
  • the wiring according to the present disclosure is a wiring manufactured by the circuit wiring manufacturing method according to the present disclosure. Moreover, as said wiring, a circuit wiring is mentioned preferably.
  • the wiring board according to the present disclosure is a substrate having wiring manufactured by the circuit wiring manufacturing method according to the present disclosure. Although the use of the wiring board which concerns on this indication is not limited, For example, it is preferable that it is a wiring board for touchscreens.
  • the input device according to the present disclosure preferably includes a circuit wiring manufactured using the photosensitive transfer material according to the present disclosure.
  • Examples of a method for producing a circuit wiring using the photosensitive transfer material according to the present disclosure include the above-described method for manufacturing a circuit wiring according to the present disclosure.
  • the input device according to the present disclosure is preferably a capacitive input device.
  • the input device according to the present disclosure is preferably an input device including a circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure.
  • the method for manufacturing an input device according to the present disclosure preferably includes the method for manufacturing a circuit wiring according to the present disclosure.
  • 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 preferably includes a circuit wiring manufactured using the photosensitive transfer material according to the present disclosure.
  • Examples of a method for producing a circuit wiring using the photosensitive transfer material according to the present disclosure include the above-described method for manufacturing a circuit wiring according to the present disclosure.
  • the touchscreen which concerns on this indication is a touchscreen which has at least the wiring manufactured by the manufacturing method of the circuit wiring which concerns on this indication.
  • the touch panel manufacturing method according to the present disclosure preferably includes the circuit wiring manufacturing method 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 is a touch panel display device having at least 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 display device manufacturing method according to the present disclosure preferably includes the circuit wiring manufacturing method according to the present disclosure, and more preferably includes the touch panel manufacturing method according to the present disclosure.
  • 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. Among these, 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
  • GG G1, G2, GFF, GF2, GF1, G1F, etc.
  • Example 1 Preparation of photosensitive resin composition 1> Each component was mixed with the following composition and the photosensitive resin composition 1 was produced.
  • composition of photosensitive resin composition 1 Specific polymer 1 (the following compound, weight average molecular weight 15,000): 9.66 parts by mass (Tg of specific polymer 1 was 40 ° C. when measured by the method described above)
  • Photoacid generator compound B below: 0.25 parts by mass
  • Surfactant compound C below
  • Additive compound D below
  • Propylene glycol monomethyl ether Acetate solvent: 90.00 parts by mass
  • each structural unit represents the content (% by mass) of each structural unit.
  • the specific polymer 1 was synthesized with reference to the descriptions in paragraphs 0155 to 0156 of JP-A-2018-031847.
  • composition of intermediate layer forming composition 1 -Pure water: 33.7 parts by mass-Methanol: 62.7 parts by mass-Hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., Metrolose 60SH-03): 3.5 parts by mass-Surfactant (DIC Corporation) Manufactured by Mega-Fac (registered trademark) F444): 0.1 parts by mass
  • the composition 1 for forming an intermediate layer is formed with a slit thickness of 3.0 ⁇ m using a slit nozzle.
  • the photosensitive resin composition 1 was applied in an amount such that the dry film thickness was 5.0 ⁇ m using a slit nozzle.
  • the film was dried with 100 ° C. warm air, and finally a polyethylene film (OSM-N, manufactured by Tredegar) was pressed as a cover film to prepare a photosensitive transfer material.
  • a cover film is peeled from the produced photosensitive transfer material, and a glass plate (manufactured by Corning, manufactured by Corning) under laminating conditions of a laminating roll temperature of 90 ° C., a linear pressure of 0.6 MPa, and a linear velocity (laminate velocity) of 3.6 m / min
  • the photosensitive transfer material was laminated to Eagle XG), and then the temporary support was peeled off from the interface with the intermediate layer to expose the intermediate layer.
  • attach a round indenter (Model No.
  • PET polyethylene terephthalate
  • the sample was left for 3 hours, and dip development was performed for 40 seconds using a 1.0% aqueous sodium carbonate solution.
  • a sample prepared in the same manner except that it was left for 24 hours after exposure was prepared.
  • the obtained line widths of the samples with different holding times were measured at five points within the substrate surface, and the average value was used as line width data.
  • (the line width of the sample left for 3 hours / the line width of the sample left for 24 hours) was used as an index value for the holding stability. It can be said that the closer the index value is to 1, the smaller the variation in line width and the higher the process suitability even when the holding time after exposure changes.
  • the index value is preferably 0.80 to 1.20, and more preferably 0.90 to 1.10.
  • the solubility is improved by stretching, so that the line becomes thin and the index value is larger than 1. Further, when the photosensitive resin layer is a negative type, the index value becomes smaller than 1 because the solubility of the photosensitive resin layer is lowered by the holding.
  • Example 2 In Example 1, a photosensitive transfer material was prepared and evaluated in the same manner as in Example 1 except that the following intermediate layer forming composition 2 was used instead of the intermediate layer forming composition 1. The evaluation results are shown in Table 1.
  • the intermediate layer forming composition 2 was prepared by the same method as the intermediate layer forming composition 1 except that the composition was changed to the following composition.
  • composition of intermediate layer forming composition 2 [Composition of intermediate layer forming composition 2] -Pure water: 33.7 parts by mass-Methanol: 62.7 parts by mass-Hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., Metrose 60SH-06): 3.5 parts by mass-Surfactant (manufactured by DIC Corporation) MegaFuck (registered trademark) F444): 0.1 parts by mass
  • Example 3 Preparation of intermediate layer forming composition 3> The intermediate layer forming composition 3 was prepared in the same manner as the intermediate layer forming composition 1 except that the composition was changed to the following composition.
  • the composition for forming an intermediate layer 1 was applied in an amount of a dry film thickness of 2.0 ⁇ m using a slit nozzle.
  • the intermediate layer forming composition 3 is dried on the intermediate layer forming composition 1 with a slit-shaped nozzle, and the total dry film thickness is 4.0 ⁇ m.
  • the photosensitive resin composition 1 was applied thereon in such an amount that the dry film thickness was 5.0 ⁇ m. Thereafter, the film was dried with 100 ° C.
  • Example 4 A polymer novolak-EVE (1-ethoxyethyl protector) having the following structure was synthesized in the same manner as in Example 1 of JP-A-2003-98671. Using the synthesized novolak resin, a positive photosensitive resin composition 2 was prepared according to the following formulation.
  • a photosensitive transfer material was produced and evaluated in the same manner as in Example 1.
  • the roll temperature during lamination was 150 ° C.
  • the lamination speed was 1 m / min.
  • a mask was used.
  • Example 5 A photosensitive transfer material was prepared and evaluated in the same manner as in Example 1 except that the intermediate layer was coated to have a dry film thickness of 4.5 ⁇ m.
  • Example 6 A photosensitive transfer material was prepared and evaluated in the same manner as in Example 1, except that the intermediate layer was coated to have a dry film thickness of 1.0 ⁇ m.
  • Example 1 a photosensitive transfer material was prepared and evaluated in the same manner as in Example 6 except that the intermediate layer forming composition 3 was used instead of the intermediate layer forming composition 1. The evaluation results are shown in Table 1.
  • Example 2 (Comparative Example 2) In Example 1, a photosensitive transfer material was prepared and evaluated in the same manner as in Example 6 except that the following intermediate layer forming composition 4 was used instead of the intermediate layer forming composition 1. The evaluation results are shown in Table 1.
  • the intermediate layer forming composition 4 was prepared by the same method as the intermediate layer forming composition 1 except that the composition was changed to the following composition.
  • Example 3 (Comparative Example 3)
  • a photosensitive transfer material was prepared and evaluated in the same manner as in Example 6 except that the following intermediate layer forming composition 5 was used instead of the intermediate layer forming composition 1.
  • the evaluation results are shown in Table 1.
  • the intermediate layer forming composition 5 was prepared by the same method as the intermediate layer forming composition 1 except that the composition was changed to the following composition.
  • Example 4 a photosensitive transfer material was prepared and evaluated in the same manner as in Example 6 except that the following intermediate layer forming composition 6 was used instead of the intermediate layer forming composition 1. The evaluation results are shown in Table 1.
  • the intermediate layer forming composition 6 was prepared by the same method as the intermediate layer forming composition 1 except that the composition was changed to the following composition.
  • the composition for forming an intermediate layer 1 was applied in an amount to give a dry film thickness of 1.0 ⁇ m using a slit nozzle.
  • the photosensitive resin composition 2 was applied in an amount such that the dry film thickness was 5.0 ⁇ m.
  • the film was dried with 100 ° C. warm air, and finally a polyethylene film (OSM-N, manufactured by Tredegar) was pressed as a cover film to prepare a photosensitive transfer material.
  • the photosensitive resin layer formed in Comparative Example 2 is a negative photosensitive resin layer.
  • the obtained photosensitive transfer material was evaluated in the same manner as in Example 1.
  • Example 101 Indium tin oxide (ITO) was deposited as a second conductive layer on a 100 ⁇ m thick PET substrate by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer by vacuum deposition. A film was formed with a thickness of 200 nm to obtain a circuit formation substrate.
  • the photosensitive transfer material obtained in Example 1 was laminated on the copper layer (linear pressure 0.8 MPa, linear velocity 3.0 m / min, roll temperature 90 ° C.). After peeling off the temporary support, the photomask is intermediated using a photomask provided with a pattern shown in FIG.
  • pattern A having a configuration in which conductive layer pads are connected in one direction. Contact exposure was performed in contact with the layer.
  • the solid line portion SL and the gray portion G are light shielding portions, and the dotted line portion DL virtually shows an alignment alignment frame. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A.
  • the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), A substrate on which copper (solid line portion SL) and ITO (gray portion G) were both drawn with the pattern A was obtained.
  • pattern alignment was performed using a photomask provided with openings of a pattern shown in FIG. 3 (hereinafter also referred to as “pattern B”) in the aligned state, and development and washing were performed.
  • the gray portion G is a light shielding portion
  • the dotted line portion DL is a virtual alignment alignment frame.
  • the copper layer was etched using Cu-02, and the remaining positive photosensitive resin layer was peeled off using a peeling solution (10% by mass sodium hydroxide aqueous solution) to obtain a circuit wiring board. As a result, a circuit wiring board was obtained. When observed with a microscope, there was no peeling or chipping, and the pattern was clean.
  • Example 102 to 106 Each of the photosensitive transfer materials obtained in Examples 2 to 6 was used and evaluated in the same manner as in Example 101. As a result, there was no peeling or chipping and the pattern was clean.

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Abstract

La présente invention concerne un matériau de transfert photosensible comprenant séquentiellement un corps de support temporaire, une couche intermédiaire et une couche de résine photosensible positive dans cet ordre, et qui est configuré de telle sorte que le corps de support temporaire et la couche intermédiaire soient en contact l'un avec l'autre et la surface de la couche intermédiaire, ladite surface étant en contact avec le corps de support temporaire, présente une dureté par pénétration de 5,0 mN ou plus ; un procédé de production d'un motif de réserve, qui utilise le matériau de transfert photosensible ; un procédé de production d'une ligne de câblage de circuit ; un panneau tactile ; et un dispositif d'affichage à écran tactile.
PCT/JP2018/044987 2018-03-29 2018-12-06 Matériau de transfert photosensible, procédé de production d'un motif de réserve, procédé de production de ligne de câblage de circuit, panneau tactile et dispositif d'affichage à écran tactile WO2019187364A1 (fr)

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JP2007140450A (ja) * 2005-10-21 2007-06-07 Hitachi Chem Co Ltd 感光性フィルム、感光性樹脂組成物、及び液晶スペーサーの製造方法。
JP2007264483A (ja) * 2006-03-29 2007-10-11 Fujifilm Corp パターン形成材料及びパターン形成方法
JP2008175957A (ja) * 2007-01-17 2008-07-31 Asahi Kasei Electronics Co Ltd 感光性樹脂積層体
JP2010060841A (ja) * 2008-09-03 2010-03-18 Fujifilm Corp 感光性転写材料、樹脂パターンの形成方法、樹脂パターン付き基板、表示装置及び液晶表示装置
US20110008733A1 (en) * 2008-03-11 2011-01-13 3M Innovative Properties Company Phototools having a protective layer
JP2012027357A (ja) * 2010-07-27 2012-02-09 Mitsubishi Paper Mills Ltd サンドブラスト用感光性フィルム
JP2017120435A (ja) * 2017-03-01 2017-07-06 富士フイルム株式会社 感光性転写材料、パターン形成方法およびエッチング方法
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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63197942A (ja) * 1986-11-14 1988-08-16 モートン　サイオコール，インコーポレイティド 感光性積層体及び画像形成方法
JP2007140450A (ja) * 2005-10-21 2007-06-07 Hitachi Chem Co Ltd 感光性フィルム、感光性樹脂組成物、及び液晶スペーサーの製造方法。
JP2007264483A (ja) * 2006-03-29 2007-10-11 Fujifilm Corp パターン形成材料及びパターン形成方法
JP2008175957A (ja) * 2007-01-17 2008-07-31 Asahi Kasei Electronics Co Ltd 感光性樹脂積層体
US20110008733A1 (en) * 2008-03-11 2011-01-13 3M Innovative Properties Company Phototools having a protective layer
JP2010060841A (ja) * 2008-09-03 2010-03-18 Fujifilm Corp 感光性転写材料、樹脂パターンの形成方法、樹脂パターン付き基板、表示装置及び液晶表示装置
JP2012027357A (ja) * 2010-07-27 2012-02-09 Mitsubishi Paper Mills Ltd サンドブラスト用感光性フィルム
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
JP2017120435A (ja) * 2017-03-01 2017-07-06 富士フイルム株式会社 感光性転写材料、パターン形成方法およびエッチング方法

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