WO2020054660A1 - Matériau de transfert photosensible, procédé de production de ligne de câblage de circuit, procédé de production de panneau tactile, procédé de production de motif de résine, et film - Google Patents

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

Info

Publication number
WO2020054660A1
WO2020054660A1 PCT/JP2019/035363 JP2019035363W WO2020054660A1 WO 2020054660 A1 WO2020054660 A1 WO 2020054660A1 JP 2019035363 W JP2019035363 W JP 2019035363W WO 2020054660 A1 WO2020054660 A1 WO 2020054660A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin layer
film
layer
photosensitive resin
transfer material
Prior art date
Application number
PCT/JP2019/035363
Other languages
English (en)
Japanese (ja)
Inventor
一真 両角
悠樹 豊嶋
漢那　慎一
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2020546006A priority Critical patent/JP7065991B2/ja
Priority to CN201980048920.1A priority patent/CN112470074A/zh
Publication of WO2020054660A1 publication Critical patent/WO2020054660A1/fr

Links

Images

Classifications

    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the present disclosure relates to a photosensitive transfer material, a method for manufacturing circuit wiring, a method for manufacturing a touch panel, a method for manufacturing a resin pattern, and a protective film.
  • a display device having a touch panel such as a capacitance type input device (for example, an organic electroluminescence (EL) display device, a liquid crystal display device, etc.), an electrode pattern corresponding to a sensor of a viewing portion, a peripheral wiring portion
  • circuit wiring such as a wiring of a take-out wiring part is provided inside the touch panel.
  • a photosensitive transfer material also called a dry film resist is being studied because the number of steps for obtaining a required pattern shape is small.
  • a protective film is usually provided on the photosensitive resin layer.
  • WO 2014/175274 has a support film, a polypropylene film, and a photosensitive layer disposed between the support film and the polypropylene film, wherein the polypropylene film is provided on the photosensitive layer side.
  • a photosensitive element is disclosed that has a first surface and a second surface opposite the first surface, wherein the first surface and the second surface are smooth.
  • Japanese Patent Application Laid-Open No. 2007-293006 discloses a photosensitive resin transfer material having, in this order, a photosensitive resin layer containing a colorant and a photosensitive resin and a cover film on a support.
  • a photosensitive resin transfer material having an intermediate layer between the film and the photosensitive resin layer and a cover film having an adhesive strength in the range of 1.5 to 8.0 g / 10 cm is disclosed.
  • JP-A-2018-2947 discloses a protective film characterized in that at least one surface has a surface average roughness (Sa) of a resin having a thickness of 15 nm or less.
  • the peelability of the protective film can be improved, for example, by providing irregularities on the surface of the protective film.
  • irregularities are provided on the surface of the protective film, the irregularities of the protective film are transferred to the surface of the photosensitive resin layer in contact with the protective film, and irregularities may be formed on the surface of the photosensitive resin layer.
  • a photosensitive resin layer having irregularities is attached to a substrate, bubbles remain between the photosensitive resin layer and the substrate, and thus a pattern failure such as a defect in a formed pattern or a defective shape occurs.
  • the positive photosensitive resin layer since the positive photosensitive resin layer usually has a high resin content, it has poor flexibility compared to the negative photosensitive resin layer.
  • the positive photosensitive resin layer which has less flexibility than the negative photosensitive resin layer, is difficult to deform following the shape of the substrate surface, so the positive photosensitive resin layer with irregularities formed on the surface is attached to the substrate. When combined, air bubbles are likely to remain between the positive photosensitive resin layer and the substrate. For this reason, the frequency of occurrence of the pattern failure becomes remarkable when a photosensitive transfer material having a positive photosensitive resin layer is applied.
  • An object of one embodiment of the present disclosure is to provide a photosensitive transfer material that is excellent in peelability of a protective film and that can reduce pattern failure. Another embodiment of the present disclosure aims to provide a method for manufacturing a circuit wiring with reduced pattern failure. Another embodiment of the present disclosure aims to provide a method for manufacturing a touch panel with reduced pattern failure. Another embodiment of the present disclosure aims to provide a method for manufacturing a resin pattern with reduced pattern failure. Another embodiment of the present disclosure aims to provide a film that is excellent in releasability and that can reduce the transfer of unevenness to the surface of an adherend.
  • Means for solving the above problems include the following aspects. ⁇ 1> A temporary support, a positive photosensitive resin layer, and a protective film are provided in this order, and the surface of the protective film on the side in contact with the positive photosensitive resin layer has the following (A) And a photosensitive transfer material satisfying (B). (A) The water contact angle is 75 ° or more. (B) The surface roughness Ra is 45 nm or less. ⁇ 2> The photosensitive transfer material according to ⁇ 1>, wherein the surface roughness Ra is 25 nm or less.
  • the protective film has a base material and an undercoat layer, and the outermost layer of the protective film on the side in contact with the positive photosensitive resin layer is the undercoat layer ⁇ 1> or ⁇ 2>
  • the photosensitive transfer material described in any one of the above.
  • ⁇ 4> a biaxially stretched film in which the protective film is a uniaxially stretched film that is a stretched product in the first stretching direction and is stretched along a film surface in a second stretching direction orthogonal to the first stretching direction; An undercoat layer that is a stretched product in the second stretching direction of the coating layer formed on one surface of the stretched film, and the protective film, the outermost layer on the side in contact with the positive photosensitive resin layer,
  • the photosensitive transfer material according to ⁇ 1> or ⁇ 2> which is the undercoat layer.
  • ⁇ 5> The photosensitive transfer material according to ⁇ 3> or ⁇ 4>, wherein the undercoat layer contains an acid-modified polyolefin.
  • ⁇ 6> The photosensitive transfer material according to ⁇ 5>, wherein the acid-modified polyolefin has an acid group, and at least one of the acid groups is an alkali metal salt.
  • ⁇ 7> The photosensitive transfer material according to any one of ⁇ 3> to ⁇ 6>, wherein the undercoat layer has a thickness of 10 nm to 550 nm.
  • ⁇ 8> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 7>, having a water-soluble resin layer between the temporary support and the positive photosensitive resin layer.
  • ⁇ 9> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 8>, wherein the positive photosensitive resin layer contains an acid-decomposable resin.
  • ⁇ 10> Any of ⁇ 1> to ⁇ 9>, wherein the positive photosensitive resin layer contains a polymer component at a ratio of 80% by mass to 98% by mass based on the total solid content of the positive photosensitive resin layer.
  • the photosensitive transfer material according to any one of the above.
  • ⁇ 11> a step of peeling off the protective film of the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 10>, and the positive photosensitive layer of the photosensitive transfer material with respect to the temporary support; Bonding the outermost layer on the side having the resin layer to the substrate having the conductive layer; pattern-exposing the positive-type photosensitive resin layer of the photosensitive transfer material after the bonding step; and A method for manufacturing circuit wiring, comprising: a step of developing the positive photosensitive resin layer after the step of forming a resin pattern to form a resin pattern; and a step of etching a substrate in a region where the resin pattern is not arranged.
  • ⁇ 12> The step of removing the protective film of the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 10>, and a positive photosensitive resin of the photosensitive transfer material with respect to the temporary support. Bonding the outermost layer on the side having the layer to the substrate having the conductive layer, pattern-exposing the positive-type photosensitive resin layer of the photosensitive transfer material after the bonding step, and performing the pattern exposure.
  • a method for manufacturing a touch panel comprising: a step of developing the positive photosensitive resin layer after the step to form a resin pattern; and a step of etching a substrate in a region where the resin pattern is not arranged.
  • ⁇ 13> a step of removing the protective film of the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 10>, and a positive photosensitive resin of the photosensitive transfer material with respect to the temporary support Bonding the outermost layer on the side having the layer to the substrate, pattern-exposing the positive-type photosensitive resin layer of the photosensitive transfer material after the bonding step, and performing the pattern-exposing step. Developing the positive photosensitive resin layer to form a resin pattern.
  • ⁇ 14> a biaxially stretched polyethylene terephthalate film in which a uniaxially stretched polyethylene terephthalate film, which is a stretched product in the first stretching direction, is stretched along a film surface in a second stretching direction orthogonal to the first stretching direction; A film formed on one surface of the polyethylene terephthalate film, the undercoat layer being a stretched product in the second stretching direction, wherein the undercoat layer satisfies the following (A) and (B).
  • A) The water contact angle is 75 ° or more.
  • the surface roughness Ra is 45 nm or less.
  • ⁇ 16> having a first resin layer and a second resin layer provided on the first resin layer, wherein the first resin layer contains polyester, and the surface of the second resin layer is A film satisfying the following (A) and (B).
  • (A) The water contact angle is 75 ° or more.
  • (B) The surface roughness Ra is 45 nm or less.
  • ⁇ 17> The film according to ⁇ 16>, wherein the thickness of the first resin layer is 5 ⁇ m to 200 ⁇ m, and the thickness of the second resin layer is 10 nm to 550 nm.
  • ⁇ 18> The film according to any one of ⁇ 14> to ⁇ 17>, which is a protective film.
  • a photosensitive transfer material that is excellent in peelability of a protective film and that can reduce pattern failure.
  • FIG. 1 is a schematic diagram illustrating an example of a layer configuration of the photosensitive transfer material according to the present disclosure.
  • FIG. 2 is a schematic diagram illustrating an example of a method for manufacturing a circuit wiring according to the present disclosure.
  • FIG. 3 is a schematic diagram showing the pattern A.
  • FIG. 4 is a schematic diagram showing the pattern B.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
  • an upper limit or a lower limit described in a certain numerical range may be replaced with an upper limit or a lower limit of another numerical range described in a stepwise manner.
  • the upper limit or the lower limit described in a certain numerical range may be replaced with the value shown in the embodiment.
  • “(meth) acryl” represents both acryl and methacryl, or either one
  • “(meth) acrylate” means both acrylate and methacrylate, or either one. .
  • the amount of each component in the composition when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, means the total amount of the plurality of substances present in the composition .
  • the term “step” includes not only an independent step but also the term as long as the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps. .
  • the notation of not indicating substituted or unsubstituted includes not only a group having no substituent but also a group 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).
  • “% by mass” and “% by weight” have the same meaning, and “parts by mass” and “parts by weight” have the same meaning.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • a chemical structural formula may be described as a simplified structural formula in which a hydrogen atom is omitted.
  • the total solid content refers to the total mass of components excluding volatile components such as solvents.
  • the photosensitive transfer material according to the present disclosure has a temporary support, a positive photosensitive resin layer, and a protective film in this order, and the surface of the protective film on the side in contact with the positive photosensitive resin layer. Satisfies the following (A) and (B).
  • (A) The water contact angle is 75 ° or more.
  • (B) The surface roughness Ra is 45 nm or less.
  • the photosensitive transfer material which concerns on this indication, it is excellent in the peelability of a protective film, and can reduce a pattern failure.
  • the reason why the photosensitive transfer material according to the present disclosure exhibits such an effect is not clear, but is presumed as follows.
  • the protective film applied to the photosensitive transfer material according to the present disclosure lowers the surface energy of the surface in contact with the positive photosensitive resin layer and reduces unevenness. Can be reduced. And since the unevenness of the surface of the protective film can be reduced, the transfer of the unevenness of the protective film to the surface of the positive photosensitive resin layer can be suppressed.
  • the photosensitive transfer material according to the present disclosure can achieve both improvement of the releasability of the protective film and reduction of the pattern failure.
  • the protective film applied to the photosensitive transfer material described in the above-mentioned WO 2014/175274 and JP-A-2007-293006 the above (A) and (B) are satisfied. It is considered impossible.
  • the photosensitive resin layer to which the protective film is applied is not a positive photosensitive resin layer.
  • FIG. 1 schematically illustrates an example of a layer configuration of the photosensitive transfer material according to the present disclosure.
  • a temporary support 12 a positive photosensitive resin layer 14, and a protective film 16 are laminated in this order.
  • the photosensitive transfer material according to the present disclosure has a temporary support.
  • the temporary support is a support that supports the positive photosensitive resin layer and can be separated from the positive photosensitive resin layer.
  • the temporary support used in the present disclosure preferably has light transmittance from the viewpoint that the positive photosensitive resin layer can be exposed through the temporary support when the positive photosensitive resin layer is subjected to pattern exposure. Having the light transmittance means that the transmittance of the main wavelength of the light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of the light used for pattern exposure is determined from the viewpoint of improving the exposure sensitivity. Therefore, it is preferably at least 60%, more preferably at least 70%.
  • the temporary support include a glass substrate, a resin film, and paper, and a resin film is particularly preferable from the viewpoint of strength, flexibility, and the like.
  • the resin film include a cycloolefin polymer film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a polyethylene terephthalate film is preferred from the viewpoint of solvent resistance and optical characteristics.
  • the thickness of the temporary support is not particularly limited, but is preferably in the range of 5 ⁇ m to 200 ⁇ m, and more preferably in the range of 10 ⁇ m to 150 ⁇ m in terms of ease of handling and versatility.
  • the thickness of the temporary support may be selected according to the material in view of the strength as the support, the flexibility required for bonding to the substrate, the light transmittance required in the first exposure step, and the like.
  • the photosensitive transfer material according to the present disclosure has a positive photosensitive resin layer.
  • the positive photosensitive resin layer used in the present disclosure is not particularly limited, and a known positive photosensitive resin layer can be used.
  • the positive photosensitive resin layer is preferably a positive photosensitive resin layer containing an acid-decomposable resin from the viewpoint of sensitivity, resolution and removability, and is preferably an acid group protected by an acid-decomposable group. More preferably, it is a chemically amplified positive photosensitive resin layer containing a polymer having a structural unit having the formula: and a photoacid generator.
  • the acid-decomposable resin is not limited as long as it is a resin that can be decomposed by the action of an acid, and examples thereof include a polymer having a structural unit having an acid group protected by an acid-decomposable group described below.
  • Photoacid generators such as onium salts and oxime sulfonate compounds described below generate an acid in response to actinic radiation (actinic rays).
  • the generated acid acts as a catalyst for the deprotection of the protected acid groups in the polymer. For this reason, the acid generated by the action of one photon contributes to a large number of deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as a power of ten. As a result, high sensitivity can be obtained.
  • the positive photosensitive resin layer is a polymer having a structural unit having an acid group protected by an acid-decomposable group (hereinafter, also referred to as “structural unit A”) (hereinafter, also simply referred to as “polymer A1”). ) Is preferable. Further, the positive photosensitive resin layer may contain another polymer in addition to the polymer A1.
  • the other polymer is a polymer that does not contain a structural unit having an acid group protected by an acid-decomposable group, as described later. Details of other polymers will be described later.
  • a polymer (including an acid-decomposable resin) contained in the positive photosensitive resin layer is collectively referred to as a “polymer component”.
  • the “polymer component” refers to the polymer A1.
  • the “polymer component” refers to both the polymer A1 and the other polymer.
  • a compound corresponding to a surfactant, a cross-linking agent, or a dispersant described below is not included in the “polymer component”.
  • the polymer A1 preferably further has a structural unit having an acid group (hereinafter, also referred to as “structural unit B”).
  • structural unit B a structural unit having an acid group
  • the polymer A1 is preferably a non-particle-shaped polymer (also referred to as a “binder polymer”) from the viewpoints of pattern shape, solubility in a developer, and transferability.
  • all of the polymers contained in the above-mentioned polymer component are each a polymer having at least a constituent unit having an acid group described below.
  • the polymer A1 is preferably an addition polymerization type resin, and more preferably a polymer having a structural unit derived from (meth) acrylic acid or (meth) acrylate.
  • the positive photosensitive resin layer is represented by a structural unit represented by the following formula A1 or a structural unit represented by the following formula A2 as a polymer component from the viewpoints of suppressing deformation of a pattern shape, solubility in a developing solution, and transferability. It is preferable to include a polymer having a structural unit and at least one structural unit selected from the group consisting of structural units represented by the following formula A3. Further, from the same viewpoint, as the polymer component, at least one selected from the group consisting of a structural unit represented by the following formula A1, a structural unit represented by the following formula A2, and a structural unit represented by the following formula A3 It is more preferable to include one kind of constituent unit and a polymer having a constituent unit having an acid group.
  • the polymer A1 contained in the positive photosensitive resin layer may be only one kind or two or more kinds.
  • preferred embodiments of the structural unit A will be described.
  • the polymer component preferably includes a polymer A1 having at least a structural unit (structural unit A) having an acid group protected by an acid-decomposable group.
  • structural unit A structural unit A
  • the polymer component contains a polymer having the structural unit A, a highly sensitive chemically amplified positive photosensitive resin layer can be obtained.
  • the “acid group protected by 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 include a carboxy group and a phenolic hydroxyl group.
  • the acid group protected by an acid-decomposable group includes a group that is relatively easily decomposed by an acid (for example, an acetal-based functional group such as a tetrahydropyranyl ester group and a tetrahydrofuranyl ester group), and is relatively hard to be decomposed by an acid.
  • Groups eg, a tertiary alkyl group such as a tert-butyl ester group, a tertiary alkyl carbonate group such as a tert-butyl carbonate group
  • the acid-decomposable group is preferably a group having a structure protected in the form of an acetal.
  • the 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.
  • structural unit A The structural unit having the acid group protected by the acid-decomposable group (structural unit A) is represented by a structural unit represented by the following formula A1, a structural unit represented by the following formula A2, and a structural unit represented by the following formula A3 It is preferably at least one type of structural unit selected from the group consisting of structural units, and from the viewpoint of sensitivity and resolution, more preferably a structural unit represented by the formula A3 described below, and more preferably a formula A3- The structural unit represented by 3 is particularly preferred.
  • R 11 and R 12 each independently represent 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, R 21 or R 22 and R 23 may be linked to form a cyclic ether, and R 24 is each independently 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 be linked to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, X 0 represents a single bond or an arylene group, 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 preferred. Each of R 11 and R 12 is 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 the 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 it is preferable that R 11 or R 12 and R 13 be 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.
  • the alkylene group may have a linear structure, a branched structure or a cyclic structure, and may have a substituent.
  • the carbon number of the alkylene group is preferably 1 to 10, more preferably 1 to 4.
  • 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.
  • the group containing R 11 to R 13 and X 1 are preferably bonded to each other at the para position.
  • R 15 represents a substituent, and is preferably an alkyl group or a halogen atom.
  • the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4.
  • 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 glass transition temperature (Tg) of the polymer A1 can be further reduced. More specifically, the content of the structural unit in which R 14 in the formula A1 is a hydrogen atom is preferably 20% by mass or more based on the total content of the structural units A contained in the polymer A1.
  • the content (content ratio: mass ratio) of the structural unit in the structural unit A in which R 14 in the formula A1 is a hydrogen atom is calculated from a 13 C-nuclear magnetic resonance spectrum (NMR) measurement by an ordinary method. It can be confirmed from the peak intensity ratio.
  • a 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 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R B12 represents a substituent
  • n Represents an integer of 0 to 4.
  • R B4 is preferably a hydrogen atom.
  • R B5 to R B11 are preferably hydrogen atoms.
  • R B12 represents a substituent, an alkyl group or a halogen atom.
  • the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4.
  • n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
  • R B4 in the structural unit of the following represents a hydrogen atom or a methyl group.
  • R 21 and R 22 are an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable.
  • R 21 and R 22 are an aryl group, a phenyl group is preferred.
  • Each of R 21 and R 22 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably one is a hydrogen atom and the other is an alkyl group having 1 to 4 carbon atoms.
  • 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 21 or R 22 and R 23 may be linked to form a cyclic ether.
  • R 24 is preferably each 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 by the same group as R 24 .
  • m is preferably 1 or 2, and more preferably 1.
  • R 31 or R 32 when R 31 or R 32 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R 31 or R 32 is an aryl group, a phenyl group is preferred. Each of R 31 and R 32 is 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 the 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 it is preferable that R 31 or R 32 and R 33 be 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 is preferably —O— from the viewpoint of exposure sensitivity.
  • the structural unit represented by the formula A3 is a structural unit having a carboxy group protected by an acid-decomposable group.
  • the polymer A1 contains the structural unit represented by the formula A3, the sensitivity during pattern formation is excellent, and the resolution is more excellent.
  • R 34 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the Tg of the polymer A1 can be further reduced. More specifically, the amount of the structural unit in which R 34 in the formula A3 is a hydrogen atom is preferably 20% by mass or more based on the total amount of the structural unit represented by the formula A3 contained in the polymer A1.
  • the content of the structural unit R 34 is a hydrogen atom in the formula A1 (content: weight ratio), 13 C-nuclear magnetic resonance spectrum (NMR) normal from the measurement It can be confirmed by the intensity ratio of the peak intensity calculated by the method.
  • the structural unit represented by the formula A3 As a structural unit having an acid group protected by an acid-decomposable group, the structural unit represented by the following formula A is more preferred from the viewpoint of further increasing the exposure sensitivity during pattern formation. preferable.
  • R 31 , R 32 , R 33 , R 34 and X 0 have the same meanings as R 31 , R 32 , R 33 , R 34 and X 0 in Formula A3, respectively, and the preferred embodiments are also the same. .
  • 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 a hydrogen atom.
  • R 34 in the structural unit of the following represents a hydrogen atom or a methyl group.
  • the structural unit A contained in the polymer A1 may be one type or two or more types.
  • the content of the structural unit A in the polymer A1 is preferably 20% by mass or more, more preferably 20% by mass to 90% by mass, and more preferably 30% by mass to the total mass of the polymer A1. More preferably, it is 70% by mass.
  • the content (content ratio: mass ratio) of the structural unit A in the polymer A1 can be confirmed by an intensity ratio of peak intensities calculated by a conventional method from 13 C-NMR measurement. Further, after all the polymer components are decomposed into constituent units (monomer units), the ratio of the constituent unit A is preferably 5% by mass to 80% by mass with respect to the total mass of the polymer components. It is more preferably from 10% by mass to 80% by mass, particularly preferably from 30% by mass to 70% by mass.
  • the polymer A1 preferably contains a structural unit having an acid group (structural unit B).
  • the structural unit B is a structural unit having an acid group not protected by a protecting group, for example, an acid group not protected by an acid-decomposable group, that is, an acid group having no protecting group.
  • the acid group in the present specification means a proton dissociable group having a pKa of 12 or less.
  • the acid group is usually incorporated into the 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 equal to or less than 10 and more preferably equal to or less than 6. Further, the pKa of the acid group is preferably -5 or more.
  • the acid group examples include a carboxy group, a sulfonamide group, a phosphono group, a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group. Among them, at least one acid group selected from the group consisting of a carboxy group and a phenolic hydroxyl group is preferable.
  • the introduction of the structural unit having an acid group into the polymer A1 can be performed by copolymerizing a monomer having an acid group or copolymerizing a monomer having an acid anhydride structure and hydrolyzing the acid anhydride. .
  • the structural unit having an acid group which is the structural unit B, is a structural unit derived from a styrene compound or a structural unit derived from a vinyl compound in which an acid group is substituted, or derived from (meth) acrylic acid. More preferably, it is a structural unit.
  • the monomer having a carboxy group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene.
  • Examples of the monomer having a phenolic hydroxyl group include p- Examples include hydroxystyrene and 4-hydroxyphenyl methacrylate, and examples of the monomer having an acid anhydride structure include maleic anhydride.
  • the structural unit B a structural unit having a carboxy group or a structural unit having a phenolic hydroxyl group is preferable from the viewpoint that sensitivity during pattern formation becomes better.
  • the monomer having an acid group capable of forming the structural unit B is not limited to the examples described above.
  • the structural unit B contained in the polymer A1 may be only one type or two or more types.
  • the polymer A1 preferably contains 0.1% to 20% by mass, and preferably 0.5% to 15% by mass of a structural unit having an acid group (structural unit B) based on the total mass of the polymer A1. More preferably, the content is 1% by mass to 10% by mass. When it is in the above range, the pattern formability will be better.
  • the content (content ratio: mass ratio) of the structural unit B in the polymer A1 can be confirmed by an intensity ratio of peak intensities calculated by a conventional method from 13 C-NMR measurement.
  • the polymer A1 does not impair the effect of the photosensitive transfer material according to the present disclosure on other structural units (hereinafter, sometimes referred to as structural units C) other than the structural units A and B described above. It may be included in the range.
  • structural units C other structural units
  • the monomer forming the structural unit C is not particularly limited, and examples thereof include styrenes, alkyl (meth) acrylate, cyclic alkyl (meth) acrylate, aryl (meth) acrylate, and unsaturated dicarboxylic 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, other Saturated compounds can be mentioned.
  • Various characteristics of the polymer A1 can be adjusted by adjusting at least one of the type and the content using the structural unit C. In particular, by appropriately using the structural unit C, the glass transition temperature of the polymer A1 can be easily adjusted. By setting the glass transition temperature to 120 ° C.
  • the positive photosensitive resin layer containing the polymer A1 can maintain good transferability and removability from the temporary support at a favorable level, while maintaining good transferability. Better resolution and sensitivity.
  • the polymer A1 may include only one type of the structural unit C, or may include two or more types of the structural unit C.
  • the structural unit C is, specifically, styrene, tert-butoxystyrene, 4-methylstyrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, ( Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ( Structural units formed by polymerizing benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, or ethylene glycol monoacetoacetate mono (meth) acrylate can be given.
  • Other examples include compounds described in paragraphs 0021
  • 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 forming these structural units include styrene, tert-butoxystyrene, 4-methylstyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) ) Isobornyl acrylate and benzyl (meth) acrylate.
  • a structural unit derived from cyclohexyl (meth) acrylate is preferably exemplified.
  • an alkyl (meth) acrylate is preferable from the viewpoint of adhesion.
  • alkyl (meth) acrylate 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, based on the total mass of the polymer A1.
  • the lower limit of the content may be 0% by mass, but the content is preferably 1% by mass or more, more preferably 5% by mass or more. When the content is in the above range, the resolution and the adhesion are further improved.
  • the polymer A1 contains, as the structural unit C, a structural unit having an ester of the acid group in the structural unit B also optimizes solubility in a developer and physical properties of the positive photosensitive resin layer. Preferred from a viewpoint.
  • the polymer A1 preferably includes, as the structural unit B, a structural unit having a carboxy group, and further includes, as a copolymerization component, a structural unit C having a carboxylate ester group.
  • the glass transition temperature (Tg) of the polymer A1 in the present disclosure is preferably 90 ° C. or less, and more preferably 20 ° C. or more and 60 ° C. or less from the viewpoint of transferability and adjusting the heating temperature in the above-described heating step. Is more preferable, and it is still more preferable that it is 30 to 50 degreeC.
  • the FOX formula is used as a guideline based on the Tg of the homopolymer of each structural unit of the target polymer A1 and the mass ratio of each structural unit. Then, a method of controlling the Tg of the desired polymer A1 can be mentioned.
  • the Tg of the homopolymer of the first structural unit contained in the copolymer 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 Tg1.
  • Tg2 K: Kelvin
  • Tg2 the mass fraction of the second structural unit in the copolymer
  • the acid value of the polymer A1 is preferably from 0 mgKOH / g to 200 mgKOH / g, more preferably from 0 mgKOH / g to 100 mgKOH / g, and more preferably from 0 mgKOH / g, from the viewpoint of developability and transferability. It is more preferably 50 mgKOH / g or less, particularly preferably 0 mgKOH / g or more and 20 mgKOH / g or less, most preferably 0 mgKOH / g or more and 10 mgKOH / g or less.
  • the acid value of the polymer in the present disclosure indicates the mass of potassium hydroxide required to neutralize the acidic component per 1 g of the polymer.
  • the resulting solution is neutralized and titrated with a 0.1 M aqueous sodium hydroxide solution at 25 ° C.
  • the acid value is calculated by the following equation using the inflection point of the titration pH curve as the end point of the titration.
  • A 56.11 ⁇ Vs ⁇ 0.1 ⁇ f / w
  • A Acid value (mgKOH / g)
  • Vs amount of 0.1 mol / L aqueous sodium hydroxide solution required for titration (mL)
  • f titer of 0.1 mol / L aqueous solution of sodium hydroxide
  • w mass (g) of a measurement sample (in terms of solid content)
  • the molecular weight of the polymer A1 is preferably 60,000 or less in terms of polystyrene equivalent weight average molecular weight. When the weight average molecular weight of the polymer A1 is 60,000 or less, the melt viscosity of the positive-type photosensitive resin layer is suppressed to be low, and bonding at a low temperature (for example, 130 ° C. or less) is realized when bonding with the substrate. be able to.
  • the weight average molecular weight of the polymer A1 is preferably from 2,000 to 60,000, and more preferably from 10,000 to 60,000.
  • the weight average molecular weight of the polymer can be measured by GPC (gel permeation chromatography), and various commercially available devices can be used as the measuring device.
  • the contents of the device and the measuring technique are as follows. It is known to those skilled in the art.
  • the weight average molecular weight was measured by gel permeation chromatography (GPC) using HLC (registered trademark) -8220 GPC (manufactured by Tosoh Corporation) as a measuring device and TSKgel (registered trademark) Super HZM-M (4) as a column.
  • Super HZ4000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ2000 (4.6 mm ID) ⁇ 15 cm, manufactured by Tosoh Corporation) connected in series, and THF (tetrahydrofuran) can be used as an eluent.
  • the measurement was performed using a differential refractive index (RI) detector with a sample concentration of 0.2% by mass, a flow rate of 0.35 mL / min, a sample injection amount of 10 ⁇ L, and a measurement temperature of 40 ° C. be able to.
  • RI differential refractive index
  • the calibration curve is "Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: "F-40", “F-20”, “F-4”, “F-1”, "A-5000”, “ A-2500 "and” A-1000 "can be produced using any of the seven samples.
  • the ratio (dispersion degree) between the number average molecular weight and the weight average molecular weight of the polymer A1 is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.
  • the production method (synthesis method) of the polymer A1 is not particularly limited, but examples thereof include a polymerizable monomer for forming the structural unit A and a polymerizable monomer for forming the structural unit B having an acid group. It can be synthesized by polymerizing a monomer and, if necessary, an organic solvent containing a polymerizable monomer for forming the other structural unit C using a polymerization initiator. Further, it can be synthesized by a so-called polymer reaction.
  • the positive photosensitive resin layer in the present disclosure from the viewpoint of developing good adhesion to the substrate and from the viewpoint of forming a high-resolution pattern, with respect to the total solid content of the positive photosensitive resin layer,
  • the polymer component is preferably contained in a proportion of 50% by mass to 99.9% by mass, more preferably in a proportion of 70% by mass to 98% by mass, and more preferably in a proportion of 80% by mass to 98% by mass. More preferably, it is particularly preferably contained in a proportion of 90% by mass to 98% by mass.
  • the positive photosensitive resin layer preferably contains the acid-decomposable resin in a proportion of 50% by mass to 99.9% by mass, and preferably 70% by mass to 9% by mass, based on the total solid content of the positive type photosensitive resin layer. It is more preferably contained in a proportion of 98% by mass, further preferably contained in a proportion of 80% by mass to 98% by mass, and particularly preferably contained in a proportion of 90% by mass to 98% by mass. Further, from the viewpoint of developing good adhesion to the substrate, the positive photosensitive resin layer contains the polymer A1 in an amount of 50% by mass to 99.99% based on the total solid content of the positive photosensitive resin layer. The content is preferably 9% by mass, more preferably 70% to 98% by mass, even more preferably 80% to 98% by mass, and 90% to 98% by mass. It is particularly preferable to include them in the ratio of
  • the positive photosensitive resin layer has, as a polymer component, a structural unit having, in addition to the polymer A1, an acid group protected with an acid-decomposable group as long as the effect of the photosensitive transfer material according to the present disclosure is not impaired.
  • another polymer may be referred to as “another polymer”.
  • the amount of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less, based on all polymer components. It is more preferably at most 20% by mass.
  • the positive photosensitive resin layer may include only one type of other polymer in addition to the polymer A1, or may include two or more types of other polymers.
  • polyhydroxystyrene can be used, and SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (all manufactured by Sartomer Co.) are commercially available.
  • ARUFON UC-3000, ARUFON UC-3510, ARUFOON UC-3900, ARUFOON UC-3910, ARUFOON UC-3920, and ARUFON UC-3080 can also be used.
  • Joncryl 690, Joncryl 78 , Joncryl 67 and Joncryl 586 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 actinic rays having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but the chemical structure is not limited.
  • a photoacid generator that is not directly sensitive to actinic light having a wavelength of 300 nm or more, if it is a compound that responds to actinic light having a wavelength of 300 nm or more by using it in combination with a sensitizer and generates an acid, is used as a sensitizer. It can be preferably used in combination.
  • a photoacid generator that generates an acid having a pKa of 4 or less is preferable
  • a photoacid generator that generates an acid having a pKa of 3 or less is more preferable
  • pKa is 2 or less.
  • Particularly preferred are photoacid generators that generate an acid.
  • the lower limit of pKa is not particularly defined.
  • the pKa is preferably, for example, -10.0 or more.
  • the photoacid generator examples include an ionic photoacid generator and a nonionic photoacid generator. Further, from the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound described below and an oxime sulfonate compound described below, and an oxime sulfonate compound. More preferably,
  • nonionic photoacid generator examples include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds.
  • the photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion.
  • These photoacid generators can be used alone or in combination of two or more.
  • trichloromethyl-s-triazines and diazomethane derivatives the compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 can be exemplified.
  • oxime sulfonate compound that is, the 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 to another atom or another group.
  • any group may be substituted, and the alkyl group in R 21 may be linear or have a branched structure. It may have a ring structure. Acceptable substituents are described below.
  • the alkyl group for R 21 a linear or branched alkyl group having 1 to 10 carbon atoms is preferable.
  • the alkyl group represented by R 21 is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group) , Preferably a bicycloalkyl group or the like) or a halogen atom.
  • the aryl group for R 21 is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a naphthyl group.
  • the aryl group for 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 also 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, and quaternary ammonium salts. Of these, onium salt compounds are preferred, and triarylsulfonium salts and diaryliodonium salts are particularly preferred.
  • ionic photoacid generators described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.
  • One photoacid generator may be used alone, or two or more photoacid generators may be used in combination.
  • the content of the photoacid generator in the positive photosensitive resin layer is 0.1% by mass to 10% by mass based on the total mass of the positive photosensitive resin layer from the viewpoint of sensitivity and resolution. Is more preferable, and more preferably 0.5% by mass to 5% by mass.
  • the positive photosensitive resin layer may contain a solvent.
  • the photosensitive resin composition for forming the positive photosensitive resin layer in order to easily form the positive photosensitive resin layer, once containing a solvent to adjust the viscosity of the photosensitive resin composition,
  • the positive photosensitive resin layer can be suitably formed by drying after applying the photosensitive resin composition containing a solvent.
  • Known solvents 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 , Diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. Further, specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP-A-2011-221494, the contents of which are incorporated herein.
  • the solvent to be added only one kind may be used, or two or more kinds may be used.
  • the solvents that can be used in the present disclosure may be used alone or in combination of two or more.
  • two or more solvents for example, a combination of propylene glycol monoalkyl ether acetates and dialkyl ethers, a combination of diacetates and diethylene glycol dialkyl ethers, or an ester and butylene glycol alkyl ether acetate It is preferable to use the compound in combination with a compound.
  • the solvent is preferably a solvent having a boiling point of 130 ° C. or more and less than 160 ° C., a solvent having a boiling point of 160 ° C. or more, or a mixture thereof. Examples of the solvent having a boiling point of 130 ° C. or more and less than 160 ° C.
  • 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 (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (boiling point 190 ° C) (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), and 1,3-butyl 3-
  • Preferred examples of the solvent include esters, ethers, and ketones described below.
  • the esters include ethyl acetate, propyl acetate, isobutyl acetate, sec-butyl acetate, isopropyl acetate, and butyl acetate.
  • ethers include diisopropyl ether, 1,4-dioxane, 1,2-dimethoxyethane, 1,3-dioxolan, propylene glycol dimethyl ether, propylene glycol monoethyl ether, and the like.
  • ketones examples include methyl n-butyl ketone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, and the like.
  • Other solvents include toluene, acetonitrile, isopropanol, 2-butanol, isobutyl alcohol and the like.
  • the content of the solvent when applying the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and more preferably 100 parts by mass, per 100 parts by mass of the total solids in the photosensitive resin composition. More preferably, it is 900 parts by mass. 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% by mass or less.
  • the positive photosensitive resin layer in the present disclosure may include a known additive as needed.
  • the positive photosensitive resin layer may contain a plasticizer for the purpose of improving plasticity.
  • the plasticizer preferably has a smaller weight average molecular weight than the polymer A1.
  • 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 even 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 A1 and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule.
  • the alkyleneoxy group contained in the plasticizer preferably has the following structure.
  • R represents an alkylene group having 2 to 8 carbon atoms
  • n represents an integer of 1 to 50
  • * represents a bonding site to another atom.
  • a positive photosensitive resin layer obtained by mixing the compound X, the polymer A1, and the photoacid generator.
  • compound X a compound having an alkyleneoxy group having the above structure
  • the plasticity is not improved as compared with the positive photosensitive resin layer formed without containing the compound X, it does not correspond to the plasticizer in the present disclosure.
  • an optionally added surfactant is not generally used in an amount that brings plasticity to the positive photosensitive resin layer, and thus does not fall under the plasticizer in the present specification.
  • plasticizer examples include compounds having the following structures, but are not limited thereto.
  • the content of the plasticizer is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 20% by mass based on the total mass of the positive photosensitive resin layer. Is more preferred.
  • the positive photosensitive resin layer may include only one type of plasticizer, or may include two or more types of plasticizers.
  • the positive photosensitive resin layer may further include a sensitizer.
  • the sensitizer absorbs actinic rays and enters an electronically excited state.
  • the sensitizer in the electronically excited state comes into contact with the photoacid generator, and causes actions such as electron transfer, energy transfer, and heat generation.
  • the photoacid generator undergoes a chemical change and is decomposed to generate an acid.
  • Exposure sensitivity can be improved by including a sensitizer.
  • anthracene derivative a compound selected from the group consisting of an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a basestyryl derivative, and a distyrylbenzene derivative is preferable, and an anthracene derivative is more preferable.
  • anthracene derivative examples include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 , 10-Dibromoanthracene, 2-ethylanthracene or 9,10-dimethoxyanthracene is preferred.
  • sensitizer examples include the compounds described in paragraphs 0139 to 0141 of WO 2015/093271.
  • the content of the sensitizer is preferably from 0% by mass to 10% by mass, more preferably from 0.1% by mass to 10% by mass, based on 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 the basic compounds used in the chemically amplified resist. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include the compounds described in paragraphs 0204 to 0207 of JP-A-2011-221494, the contents of which are incorporated herein.
  • examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, and triethanolamine.
  • examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
  • examples of the aromatic amine 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 a carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
  • the above basic compounds may be used alone or in combination of two or more.
  • 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 based on 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.
  • the heterocyclic compound in the present disclosure is not particularly limited.
  • the positive photosensitive resin layer includes, for example, compounds having an epoxy group or an oxetanyl group in the molecule described below, heterocyclic compounds containing an alkoxymethyl group, various cyclic ethers, oxygen-containing monomers such as cyclic esters (lactones); cyclic amines And nitrogen-containing monomers such as oxazoline; and heterocyclic monomers having d electrons such as silicon, sulfur and phosphorus.
  • the content of the heterocyclic compound is 0.01% by mass to 50% by mass based on the total mass of the positive photosensitive resin layer. Is preferably 0.1% by mass to 10% by mass, and more preferably 1% by mass to 5% by mass. The above range is preferable from the viewpoint of adhesion and etching resistance.
  • One heterocyclic compound may be used alone, or two or more heterocyclic compounds may be used in combination.
  • Specific examples of the compound having an epoxy group in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, and aliphatic epoxy resin.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolak type epoxy resin and aliphatic epoxy resin are more preferable, and aliphatic epoxy resin is particularly preferable.
  • the compound having an oxetanyl group in the molecule include Alonoxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, and PNOX (these are Toagosei Co., Ltd.) (Manufactured by K.K.).
  • the compound containing an oxetanyl group is used alone or in combination 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, ⁇ -glycidoxypropyltriakoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, ⁇ -methacryloxy Propyl trialkoxysilane, ⁇ -methacryloxypropylalkyl dialkoxysilane, ⁇ -chloropropyl trialkoxysilane, ⁇ -mercaptopropyl trialkoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyl trialkoxysilane, vinyl trialkoxysilane Is mentioned.
  • ⁇ -glycidoxypropyl trialkoxysilane and ⁇ -methacryloxypropyl trialkoxysilane are more preferable, ⁇ -glycidoxypropyl trialkoxysilane 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 uniformity of the film thickness.
  • a surfactant any of an anionic surfactant, a cationic surfactant, a nonionic surfactant (nonionic surfactant), and an amphoteric surfactant can be used, but a preferred surfactant is used.
  • the surfactant is a non-ionic surfactant. Examples of the nonionic surfactant 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, manufactured by DIC Corporation
  • Florard Manufactured by Sumitomo 3M Limited
  • Asahi Guard registered trademark, manufactured by Asahi Glass Co., Ltd.
  • Surflon registered trademark, manufactured by Asahi Glass Co., Ltd.
  • PolyFox manufactured by OMNOVA
  • SH-8400 Toray Dow) Corning Co., Ltd.
  • the surfactant contains a structural unit SA and a structural unit SB represented by the following formula I-1 and has a weight average in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
  • a copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferable example.
  • 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 1 carbon atom
  • L represents an alkylene group having 3 or more and 6 or less carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p represents a numerical value of 10 mass% or more and 80 mass% or less
  • Q represents a numerical value of 20% by mass or more and 90% by mass or less
  • r represents an integer of 1 or more and 18 or less
  • s represents an integer of 1 or more and 10 or less
  • * 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 surface to be coated, and has 2 or more carbon atoms. 3 alkyl groups are more preferred.
  • the weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.
  • One surfactant may be used alone, or two or more surfactants may be used in combination.
  • the amount of the surfactant added is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and more preferably 0.1% by mass or less with respect to the total mass of the positive photosensitive resin layer. More preferably, the content is from 01% by mass to 3% by mass.
  • metal oxide particles In the positive photosensitive resin layer of the present disclosure, metal oxide particles, an antioxidant, a dispersant, an acid multiplying agent, a development accelerator, a conductive fiber, a coloring agent, a thermal radical polymerization initiator, a thermal acid generator, Known additives such as an ultraviolet absorber, a thickener, a crosslinking agent, and an organic or inorganic suspending agent can be further added. Preferred embodiments of the other components are described in paragraphs 0165 to 0184 of JP-A-2014-85643, respectively, and the contents of this publication are incorporated herein.
  • a composition can be prepared by preparing a solution in which each component is dissolved in a solvent in advance, and then mixing the obtained solution at a predetermined ratio.
  • the composition prepared as described above can be used after being filtered using a filter having a pore size of 0.2 ⁇ m or the like.
  • the solid components (for example, a polymer component, a photoacid generator, a basic compound, and a surfactant) in the photosensitive resin composition used in the present disclosure are uniform in the thickness of the positive photosensitive resin layer, In order to improve shape unevenness and the like, it is preferable to adjust by dissolving in the above-mentioned solvent.
  • a positive photosensitive resin layer can be formed by applying the photosensitive resin composition on a temporary support and drying it.
  • the coating method is not particularly limited, and coating can be performed by a known method such as slit coating, spin coating, curtain coating, or inkjet coating.
  • the photosensitive resin composition can be applied after forming an intermediate layer described later on the temporary support.
  • the photosensitive transfer material according to the present disclosure has a protective film.
  • the surface of the protective film on the side in contact with the positive photosensitive resin layer satisfies the following (A) and (B).
  • the water contact angle is 75 ° or more.
  • the surface roughness Ra is 45 nm or less.
  • the surface of the protective film that is in contact with the positive photosensitive resin layer means the surface of the protective film to be bonded to the positive photosensitive resin layer (that is, the contact surface). Then, it means the surface of the protective film that is exposed by being separated from the positive photosensitive resin layer (that is, the peeled surface). Specific peeling conditions are as described below.
  • the photosensitive transfer material according to the present disclosure is peelable at the interface between the protective film and the positive photosensitive resin layer.
  • peelable at the interface between the protective film and the positive photosensitive resin layer means that the protective film can be peeled from the positive photosensitive resin layer under the following peeling conditions.
  • the photosensitive transfer material according to the present disclosure the protective film undercoat layer and the positive photosensitive resin layer At the interface with The presence of the undercoat layer in the peeled protective film can be confirmed by observing the cross section of the protective film.
  • the cross section of the protective film peeled off from the positive photosensitive resin layer under the following peeling conditions is observed using a scanning electron microscope.
  • a laminated structure including the base material of the protective film is observed in the observed image, it can be determined that the protective film has an undercoat layer.
  • the photosensitive transfer material is cut out to 4.5 cm wide by 9 cm long, and the surface on the temporary support side is stuck on a glass plate with a double-sided adhesive tape.
  • One end of the tape is gripped, and 180 ° peeling is performed at a peeling speed of 500 mm / min using a tensile tester.
  • the pressure-sensitive adhesive tape and the double-sided pressure-sensitive adhesive tape used are those described in JIS Z 0109: 2015, and the tensile tester is a tensile tester (tester grade 1: relative indication error) specified in JIS B 7721: 2009. ⁇ 1.0%) or equivalent tensile tester is used.
  • the water contact angle of the surface of the protective film on the side in contact with the positive photosensitive resin layer is 75 ° or more. By adjusting the water contact angle within the above numerical range, since the surface energy of the surface of the protective film on the side in contact with the positive photosensitive resin layer can be reduced, the peelability of the protective film can be improved. .
  • the water contact angle is preferably 78 ° or more, more preferably 82 ° or more, and may be 85 ° or more, or may be 100 ° or more, from the viewpoint of peelability.
  • the upper limit of the water contact angle is not limited.
  • the water contact angle is preferably 150 ° or less, and more preferably 120 ° or less, from the viewpoint of adhesion.
  • the water contact angle can be measured by the following method. Using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DROPMASTER-501), the contact angle measured 7 seconds after 2 ⁇ L of purified water was dropped on the measurement surface at a temperature of 25 ° C. I do. When the protective film and the positive photosensitive resin layer are in contact with each other, the water contact angle is measured using the peeled surface exposed by peeling the protective film under the above peeling conditions as a measurement surface.
  • a contact angle meter manufactured by Kyowa Interface Science Co., Ltd., DROPMASTER-501
  • the surface roughness Ra of the surface of the protective film on the side in contact with the positive photosensitive resin layer is 45 nm or less.
  • the surface roughness Ra is preferably 42 nm or less, more preferably 25 nm or less, further preferably 20 nm or less, and particularly preferably 14 nm or less.
  • the lower limit of the surface roughness Ra is not limited.
  • the surface roughness Ra is preferably 1 nm or more from the viewpoint of manufacturing.
  • the surface roughness Ra can be measured by the following method. With respect to the measurement surface of the protective film, a surface profile of the protective film is obtained using a three-dimensional optical profiler (New View 7300, manufactured by Zygo) under the following conditions.
  • the measurement and analysis software uses MicroScope Application 8.3.2.
  • a Surface Map screen is displayed by the analysis software (MetroPro 8.3.2-Microscope Application), and histogram data is obtained in the Surface Map screen.
  • the arithmetic average roughness is calculated from the obtained histogram data, and is set as the Ra value.
  • the surface roughness Ra is measured using the peeled surface exposed by peeling the protective film under the above peeling conditions as a measurement surface.
  • a resin film is preferable.
  • the resin film include a polyolefin film (eg, a polypropylene film), a polyester film (eg, a polyethylene terephthalate film), a cellulose triacetate film, a polycarbonate film, a polystyrene film, and the like.
  • a polyolefin film is preferable, and a polypropylene film is more preferable as the base material of the protective film, from the viewpoints of peelability and reduction of pattern failure.
  • polypropylene film a commercially available product may be used, and for example, Trefane (registered trademark) 25KW37 (manufactured by Toray Industries, Inc.) or the like may be used.
  • a polyester film is preferable, and a polyethylene terephthalate film is more preferable.
  • the resin film may be an unstretched film or a stretched film, but is preferably a stretched film.
  • the stretched film may be a uniaxially stretched film, may be a biaxially stretched film, may be a multiaxially stretched film such as triaxially stretched, but is preferably a biaxially stretched film, From the viewpoint of smoothness, a biaxially oriented polypropylene film or a biaxially oriented polyethylene terephthalate film is more preferable.
  • the thickness of the substrate is not particularly limited, but is preferably in the range of 5 ⁇ m to 200 ⁇ m, and more preferably in the range of 10 ⁇ m to 150 ⁇ m.
  • the protective film has a base material and an undercoat layer, and the outermost layer of the protective film on the side in contact with the positive photosensitive resin layer is preferably the above-mentioned undercoat layer. Since the surface energy of the protective film can be reduced by having the undercoat layer, the peelability of the protective film can be improved.
  • the base material in the protective film is a resin film
  • the undercoat layer may be formed on an unstretched film, may be formed on a uniaxially stretched film, or may be formed on a biaxially stretched film. Is also good.
  • the undercoat layer may be a stretched product stretched together with the unstretched film serving as the base material, or a stretched product stretched together with the uniaxially stretched film serving as the base material, from the viewpoint of adhesion to the base material. You may.
  • the undercoat layer, which is a stretched product can be formed, for example, by stretching a coating layer formed on a resin film as a base material together with the resin film, as described later.
  • the protective film is a biaxially stretched film in which a uniaxially stretched film, which is a stretched product in the first stretching direction, is stretched along a film surface in a second stretching direction orthogonal to the first stretching direction;
  • An undercoat layer that is a stretched product of the coating layer formed on one surface of the stretched film in the second stretching direction (hereinafter, may be simply referred to as “undercoat layer that is a stretched product”), and is a protective film.
  • the outermost layer on the side in contact with the positive photosensitive resin layer is preferably the undercoat layer.
  • the surface energy of the protective film can be reduced to improve the peelability of the protective film, and further, the smoothness of the protective film surface and the base material ( That is, the adhesion between the biaxially stretched film) and the undercoat layer can be improved.
  • the “biaxially stretched film” in the protective film having a biaxially stretched film and an undercoat layer that is a stretched product has a surface roughness Ra of one surface measured by the method described above of 45 nm.
  • the following resin films are referred to.
  • the “undercoat layer that is a stretched product” refers to a material having an adhesive force with a biaxially stretched film measured by the following method of 0.098 N / cm or more.
  • the method for measuring the adhesion between the biaxially stretched film and the undercoat layer will be described below.
  • a tape (Printerc C, manufactured by Nitto Denko Corporation) is attached to the surface of the protective film having an undercoat layer on the undercoat layer side, and cut into 4.5 cm ⁇ 9 cm so that the width of the tape and the protective film match.
  • the tape is peeled at 180 ° at a peeling speed of 500 mm / min using a Tensilon universal tester (manufactured by A & D Corporation), and the adhesion is measured.
  • the undercoat layer preferably contains a modified resin, and more preferably contains at least one resin selected from the group consisting of an acid-modified resin and a silicone-modified resin, from the viewpoint of reducing releasability and pattern failure. .
  • the undercoat layer preferably contains at least one resin selected from the group consisting of a modified polyolefin and a modified acrylic polymer, from the viewpoint of reducing releasability and pattern failure, and comprises an acid-modified polyolefin and More preferably, it contains at least one resin selected from the group consisting of silicone-modified acrylic polymers, and particularly preferably it contains acid-modified polyolefin.
  • the acid-modified polyolefin is not limited as long as it is an acid-modified polyolefin, and is, for example, a terminal-modified or graft-modified polyolefin using a compound having an acid group (for example, an unsaturated carboxylic acid or the like) or an anhydride thereof. And the like.
  • the acid group include a carboxy group, a sulfo group, and a phosphono group.
  • At least one of the acid groups contained in the acid-modified polyolefin is preferably in the form of a salt (ie, a salt of an acid group).
  • a salt ie, a salt of an acid group.
  • the salt include an alkali metal salt (for example, a sodium salt, a potassium salt, a lithium salt and the like), an amine salt, an ammonium salt and the like.
  • at least one of the acid groups in the acid-modified polyolefin is preferably an alkali metal salt, and more preferably a sodium salt, from the viewpoint of the pattern shape.
  • polyolefins such as acid-modified polyolefins may be used.
  • Chemipearl registered trademark
  • S100, S120, S200, S300, S650, SA100 all manufactured by Mitsui Chemicals, Inc.
  • Hardlen registered trademark
  • NZ1004, NZ1005 all manufactured by Toyobo Co., Ltd.
  • Arrowbase registered trademark
  • Seixen registered trademark
  • AC A, L, NC, N
  • Sepolsion registered trademark
  • G315, VA407 all manufactured by Sumitomo Seika Co., Ltd.
  • Hitec S3121, S3148K all manufactured by Toho Chemical Co., Ltd.
  • Examples of the acid-modified polyolefin in which at least one of the acid groups is an amine salt include, for example, Sixen (registered trademark) L and the like.
  • Examples of the acid-modified polyolefin in which at least one of the acid groups is an ammonium salt include, for example, Sixen (registered trademark) AC.
  • Examples of the acid-modified polyolefin in which at least one of the acid groups is a sodium salt include Sixen (registered trademark) NC, Chemipearl (registered trademark) S120, and the like.
  • Silicone-modified acrylic polymer is an acrylic polymer having a silicone moiety.
  • the silicone-modified acrylic polymer is not limited, and a known one can be used.
  • a commercially available product may be used as the silicone-modified acrylic polymer, and examples thereof include Cymac (registered trademark) US-450 and US-480 (all manufactured by Toagosei Co., Ltd.).
  • the resin contained in the undercoat layer may be used alone or in combination of two or more.
  • the content of the resin in the undercoat layer is preferably from 50% by mass to 100% by mass, and more preferably from 80% by mass to 100% by mass, based on the total mass of the undercoat layer, from the viewpoint of the releasability and the reduction in pattern failure. Is more preferable.
  • the total content of at least one resin selected from the group consisting of the modified polyolefin and the modified acrylic polymer in the undercoat layer is, with respect to the total weight of the undercoat layer, from the viewpoint of reducing releasability and pattern failure. , 50% by mass to 100% by mass, more preferably 80% by mass to 100% by mass.
  • the weight average molecular weight of the resin contained in the undercoat layer is preferably from 1,000 to 500,000 in terms of polystyrene in terms of releasability.
  • the weight average molecular weight of the resin contained in the undercoat layer can be measured by the method described in the section of “Positive photosensitive resin layer” above.
  • the undercoat layer may further contain various additives as necessary.
  • the additive include a surfactant, a crosslinking agent, an antioxidant, a preservative, and the like.
  • the surfactant examples include known surfactants such as a cationic surfactant, a nonionic surfactant, and an anionic surfactant. Among these, as the surfactant, an anionic surfactant is preferable.
  • anionic surfactants include Lapizol (registered trademark) A-90, A-80, BW-30, B-90, and C-70 (all manufactured by NOF Corporation), and NIKKOL (registered trademark).
  • OTP-100 (all manufactured by Nikko Chemical Co., Ltd.), Kohakuur (registered trademark) ON, L-40, Phosphanol (registered trademark) 702 (all manufactured by Toho Chemical Industry Co., Ltd.), Beaulite (registered trademark) ) A-5000, SSS (all manufactured by Sanyo Chemical Industries, Ltd.) and the like.
  • crosslinking agent examples include known crosslinking agents such as epoxy, isocyanate, melamine, carbodiimide, and oxazoline.
  • the thickness of the undercoat layer is not limited, and is preferably from 10 nm to 550 nm, more preferably from 10 nm to 500 nm, still more preferably from 10 nm to 100 nm, from the viewpoint of reducing peeling and pattern failure. It is particularly preferably from 10 nm to 60 nm.
  • the method for forming the undercoat layer is not limited.
  • an undercoat layer can be formed by applying a coating liquid for forming an undercoat layer containing a solid content of the undercoat layer on a base material and drying.
  • the coating method is not limited, and a known method such as slit coating, spin coating, curtain coating, or inkjet coating can be applied.
  • the drying method is not limited, and a known method such as a heater or hot air can be applied.
  • the undercoat layer may be formed by an inline coating method using a coating solution for forming an undercoat layer.
  • the in-line coating method is a method of applying a coating liquid for forming an undercoat layer at a stage before winding the manufactured base material, and an off-line coating method of separately applying after winding the manufactured base material.
  • an undercoat layer by an inline coating method one surface of a resin film stretched in the first stretching direction was coated with an undercoat layer formation coating solution, and the undercoat layer formation coating solution was applied.
  • a method of forming an undercoat layer by stretching the resin film in a second stretching direction orthogonal to the first stretching direction along the resin film surface is preferable. By stretching in the second stretching direction in a state where the undercoat layer forming coating liquid is applied to one surface of the resin film stretched in the first stretching direction, the adhesion between the resin film and the undercoat layer serving as the base material is improved. And the smoothness of the protective film surface can be improved.
  • the stretching method is not limited, and a known method can be applied.
  • the stretching temperature may be appropriately selected according to the glass transition temperature (Tg) of the substrate, and is preferably equal to or higher than Tg, and is equal to or lower than 80 ° C. higher than Tg, and is higher by 5 ° C. than Tg. It is more preferable that the temperature is equal to or higher than the temperature and equal to or lower than the temperature higher by 60 ° C. than the Tg.
  • the stretching ratio is preferably 2.5 times to 5.0 times, more preferably 3.0 times to 4.5 times.
  • the stretching ratio refers to the ratio of the length after stretching to the length before stretching. After the biaxial stretching, the stretched film may be subjected to heat treatment such as heat setting and thermal relaxation.
  • the protective film may have an overcoat layer on the outermost layer on the side opposite to the side in contact with the positive photosensitive resin layer.
  • the overcoat layer for example, the slipperiness with a mask used at the time of exposure can be improved.
  • the resin contained in the overcoat layer examples include polyolefin, acrylic polymer, polyester, polyurethane, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl pyrrolidone, polyvinyl acetal, polyvinyl alcohol, polyamide, butadiene-styrene thermoplastic polymer, Epoxy resins, melamine resins and the like can be mentioned.
  • an acrylic polymer is preferable as the resin contained in the overcoat layer from the viewpoint of slipperiness. It is preferable that a surfactant, a wax, a matting agent, resin particles, inorganic particles, and the like are further added to the overcoat layer from the viewpoint of slipperiness.
  • the overcoat layer preferably contains inorganic particles.
  • the particle diameter of the inorganic particles is preferably in the range of 0.03 ⁇ m to 1 ⁇ m, more preferably in the range of 0.05 ⁇ m to 0.5 ⁇ m.
  • the thickness of the overcoat layer is not limited, and is preferably from 10 nm to 500 nm, and more preferably from 10 nm to 100 nm, from the viewpoint of slipperiness.
  • the photosensitive transfer material according to the present disclosure may have an intermediate layer between the temporary support and the positive photosensitive resin layer.
  • a water-soluble resin layer is preferable. By having the water-soluble resin layer, the adhesion between the temporary support and the positive photosensitive resin layer can be improved.
  • the water-soluble resin layer is a layer containing a water-soluble resin.
  • the water-soluble resin is not limited as long as it is a water-soluble resin, and examples thereof include polyvinyl alcohol, cellulose, polyacrylamide, polyethylene oxide, vinyl ether, polyamide, and copolymers thereof. Among these, cellulose is preferable as the water-soluble resin from the viewpoint of adhesion.
  • water-soluble means a property of dissolving 1 g or more in 100 g of water at 25 ° C.
  • the content of the water-soluble resin in the water-soluble resin layer is preferably 20% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass based on the total mass of the water-soluble resin layer. % Is more preferable.
  • the thickness of the water-soluble resin layer is preferably from 1 ⁇ m to 10 ⁇ m, more preferably from 1 ⁇ m to 5 ⁇ m, from the viewpoint of adhesion.
  • the surface of the protective film on the side in contact with the positive photosensitive resin layer may be subjected to surface modification from the viewpoint of peelability.
  • the surface modification method is not limited as long as the surface energy of the protective film is reduced, and examples thereof include a corona treatment, a plasma treatment, a laser treatment, and an ultraviolet treatment.
  • the method for manufacturing a circuit wiring according to the present disclosure includes a step of peeling the protective film of the photosensitive transfer material (hereinafter, may be referred to as a “peeling step”) and a step of removing the protective film of the photosensitive transfer material from the temporary support.
  • peeling step a step of peeling the protective film of the photosensitive transfer material
  • bonding step a step of bonding the outermost layer on the side having the positive photosensitive resin layer to the substrate having the conductive layer
  • a step of pattern-exposing the positive photosensitive resin layer of the transfer material (hereinafter, may be referred to as an “exposure step”), and developing the positive photosensitive resin layer after the pattern exposure step to form a resin pattern. (Hereinafter, may be referred to as “development step”) and a step of etching the substrate in a region where the resin pattern is not disposed (hereinafter, referred to as “etching step”). That it includes. A), the. According to the method for manufacturing a circuit wiring according to the present disclosure, since the photosensitive transfer material is used, a circuit wiring with reduced pattern failure can be manufactured.
  • the method for manufacturing a circuit wiring according to the present disclosure includes a step of peeling off the protective film of the photosensitive transfer material.
  • the method for peeling the protective film is not limited, and a known method can be applied.
  • the method for manufacturing a circuit wiring according to the present disclosure includes a step of bonding the outermost layer of the photosensitive transfer material having the positive photosensitive resin layer to the temporary support to a substrate having a conductive layer. .
  • the substrate 20 (circuit wiring forming substrate) has a base material 22 and a plurality of conductive layers including a first conductive layer 24 and a second conductive layer 26 having different constituent materials.
  • the positive photosensitive resin layer 14 of the photosensitive transfer material 100 is brought into contact with the first conductive layer 24 and bonded to the substrate 20 (substrate for forming circuit wiring). Note that such bonding of the circuit wiring forming substrate and the photosensitive transfer material may be referred to as “transfer” or “laminate”.
  • Lamination of the photosensitive transfer material to the substrate is performed by superposing the outermost layer of the photosensitive transfer material on the side having the positive photosensitive resin layer with respect to the temporary support on the substrate, and applying pressure and heating using a roll or the like. It is preferably performed.
  • a known laminator such as a laminator, a vacuum laminator, or an auto-cut laminator that can further increase the productivity can be used.
  • the base material constituting the substrate is a resin film, it is also possible to perform roll-to-roll bonding.
  • the substrate has a conductive layer on a substrate such as glass, silicon, or a film, and an optional layer may be formed as necessary.
  • the substrate is transparent.
  • the base material preferably has a refractive index of 1.50 to 1.52.
  • the base material may be composed of a light-transmitting base material such as a glass base material, and tempered glass represented by gorilla glass of Corning and the like can be used. Further, as the above-mentioned transparent substrate, the materials used in JP-A-2010-86684, JP-A-2010-152809 and JP-A-2010-257492 can be preferably used.
  • a film substrate When a film substrate is used as the substrate, it is more preferable to use a substrate having small optical distortion and a substrate having high transparency, and a resin film is more preferable.
  • Specific materials include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.
  • the substrate is preferably a glass substrate or a film substrate, more preferably a film substrate, and particularly preferably a resin film.
  • the substrate is a sheet-shaped resin composition.
  • any conductive layer used for general circuit wiring or touch panel wiring can be exemplified.
  • the conductive layer is preferably a metal layer, and at least one layer selected from the group consisting of conductive metal oxide layers, from the viewpoint of conductivity and fine line forming properties, and is a metal layer. Is more preferable, and a copper layer is particularly preferable.
  • the base material may have one conductive layer or two or more conductive layers. In the case of two or more layers, it is preferable to have conductive layers of different materials. Examples of the material of the conductive layer include a metal and a conductive metal oxide. Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, and Mo.
  • conductive metal oxide examples include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO 2 .
  • conductive in the present disclosure refers to a volume resistivity of less than 1 ⁇ 10 6 ⁇ cm, and preferably a volume resistivity of less than 1 ⁇ 10 4 ⁇ cm.
  • the conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition unit used in a capacitive touch panel, or a wiring of a peripheral extraction unit.
  • the method for manufacturing a circuit wiring according to the present disclosure includes a step of pattern-exposing the positive photosensitive resin layer of the photosensitive transfer material after the bonding step.
  • FIG. 2 (b) schematically shows an example of the exposure step.
  • the positive photosensitive resin layer 14 is subjected to pattern exposure via the temporary support 12 of the photosensitive transfer material.
  • a mask 30 having a predetermined pattern is disposed above the photosensitive transfer material 100 disposed on the first conductive layer 24 (the side opposite to the side in contact with the first conductive layer 24), and thereafter, the mask 30 And a method of exposing to ultraviolet light from above the mask through the mask.
  • the detailed arrangement and specific size of the pattern are not particularly limited.
  • a display device for example, a touch panel
  • an input device having circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure
  • At least a part is preferably a fine line of 100 ⁇ m or less, and more preferably a fine line of 70 ⁇ m or less.
  • the light source used for the exposure can be appropriately selected and used as long as the exposed portion of the positive photosensitive resin layer can be irradiated with light (for example, 365 nm, 405 nm, etc.) in a wavelength range that can be dissolved in the developer.
  • light for example, 365 nm, 405 nm, etc.
  • an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp and the like can be mentioned.
  • the exposure amount is preferably from 5mJ / cm 2 ⁇ 200mJ / cm 2, more preferably 10mJ / cm 2 ⁇ 100mJ / cm 2.
  • pattern exposure may be performed after the temporary support is separated from the photosensitive resin layer, and before the temporary support is separated, pattern exposure is performed through the temporary support, and then the temporary support is separated. May be.
  • the pattern exposure may be exposure through a mask or digital exposure using a laser or the like.
  • the method for manufacturing a circuit wiring according to the present disclosure includes a step of forming a resin pattern by developing the positive photosensitive resin layer after the step of pattern exposure.
  • FIG. 2C schematically shows an example of the developing step.
  • the temporary support 12 is separated from the positive photosensitive resin material layer 14 after the exposure step, and then the positive photosensitive resin layer 14 after the exposure step is developed to form a first pattern 14A.
  • the development of the pattern-exposed positive photosensitive resin layer can be performed using a developer.
  • the developer is not particularly limited as long as the exposed portion of the positive photosensitive resin layer can be removed.
  • a known developer such as a developer described in JP-A-5-72724 may be used. it can.
  • the developing solution is preferably a developing solution in which the exposed portion of the photosensitive resin layer has a developing behavior of a dissolving type.
  • an alkali aqueous solution-based developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L is preferable.
  • the developer may further contain an organic solvent miscible with water, a surfactant, and the like.
  • a developer described in paragraph 0194 of International Publication No. 2015/093271 is exemplified.
  • the development system is not particularly limited, and may be any of paddle development, shower development, shower and spin development, and dip development.
  • shower development will be described.
  • the exposed portion can be removed.
  • the liquid temperature of the developer is preferably from 20 ° C to 40 ° C.
  • the method may include a post-baking step of heating a pattern including the photosensitive resin layer obtained by development.
  • Post-baking is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably in an environment of 506.6 kPa or more.
  • the heating of the post bake is more preferably performed in an environment of 114.6 kPa or less, and particularly preferably performed in an environment of 101.3 kPa or less.
  • the post-baking temperature is preferably from 80 ° C. to 250 ° C., more preferably from 110 ° C. to 170 ° C., and particularly preferably from 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.
  • Post-baking may be performed in an air environment or in a nitrogen-substituted environment.
  • steps such as a post-exposure step may be provided before the etching step described later.
  • the method of manufacturing a circuit wiring according to the present disclosure includes a step of etching a substrate in a region where the resin pattern is not arranged.
  • FIG. 2 An example of the etching step is schematically shown in FIG.
  • the etching step at least the first conductive layer 24 and the second conductive layer 26 of the plurality of conductive layers in the region where the first pattern 14A is not arranged are etched.
  • a first conductive layer 24A and a second conductive layer 26A having the same pattern as the first pattern 14A are formed.
  • etching treatment As a method of the etching treatment, a known method such as a method described in paragraphs 0048 to 0054 of JP-A-2010-152155, a known dry etching method such as plasma etching, or the like can be applied.
  • an acidic type or alkaline type etchant may be appropriately selected in accordance with an etching target.
  • the acidic type etchant include an aqueous solution of an acidic component alone such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and a mixed aqueous solution of an acidic component and a salt such as ferric chloride, ammonium fluoride, and potassium permanganate. Illustrated.
  • the acidic component a component obtained by combining a plurality of acidic components may be used.
  • the alkaline type etchant include aqueous solutions of alkali components alone such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, salts of organic amines such as tetramethylammonium hydroxide, and alkali components and potassium permanganate. Examples thereof include a mixed aqueous solution with a salt.
  • 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 resin pattern used as the etching mask preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower. Therefore, peeling of the positive photosensitive resin layer during the etching step is prevented, and a portion where the positive photosensitive resin layer does not exist is selectively etched.
  • a washing step and a drying step may be performed as necessary to prevent contamination of the process line.
  • the cleaning liquid used in the cleaning step pure water, an organic solvent soluble in pure water, or an aqueous solution in which a surfactant is mixed can be used. From the viewpoint of suppressing peeling unevenness due to droplets remaining on the substrate surface and improving removability, it is preferable to use an organic solvent that can be dissolved in pure water, or an aqueous solution in which a surfactant is mixed, as the cleaning liquid. It is more preferable to use an aqueous solution in which both an organic solvent soluble in water and a surfactant are mixed.
  • the water-soluble organic solvent to be mixed with water is not particularly limited, but preferably has a boiling point of 50 ° C to 250 ° C, more preferably 55 ° C to 200 ° C, from the viewpoint of the volatility of the solvent. More preferably, the temperature is from 60 ° C to 150 ° C.
  • the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, and ethylene glycol, 2-acetoxy-2-phenylethanol, 3-methoxy-3-methylethanol, and 3-methoxy-3-methylethanol.
  • methanol, ethanol, propanol, isopropanol, 3-methoxy-3-methylbutanol, 2-acetoxy-2-phenylethanol, tetrahydrofuran, and dimethylsulfoxide are preferred.
  • the water-soluble organic solvent to be mixed with water may be used alone or in combination of two or more.
  • the content of the water-soluble organic solvent to be mixed with water is preferably 0.01% by mass to 95% by mass, and more preferably 0.01% by mass to 20% by mass, based on the total mass of the aqueous solution. More preferably, the content is 0.01% by mass to 10% by mass, and particularly preferably 0.01% by mass to 5% by mass.
  • the surfactant to be mixed with water is not particularly limited as long as it is water-soluble, and an anionic surfactant, a cationic surfactant, a nonionic surfactant (nonionic surfactant), or Any of the amphoteric surfactants can be used. From the viewpoint of suppressing foaming of the cleaning liquid, a nonionic surfactant is preferable.
  • the anionic surfactant include carboxylate, sulfonate, sulfate, phosphate and the like.
  • the cationic surfactant include amine salts and quaternary ammonium salts.
  • amphoteric surfactants include betaine types.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, alkylbenzene polyalkylene glycols, polyoxyalkylene glycols, and silicone-based surfactants. Activators and fluorinated surfactants can be mentioned.
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • F-top manufactured by JEMCO
  • Megafac manufactured by DIC
  • Florard Suditomo 3M
  • Surflon made by Asahi Glass Co., Ltd.
  • PolyFox made by OMNOVA
  • Surfynol made by Nissin Chemical Industry Co., Ltd.
  • SH-8400 Toray Dow Corning Co., Ltd.
  • the surfactant may be used alone, or two or more surfactants may be used in combination, and it is preferable to use two or more surfactants in combination.
  • the content of the surfactant mixed with water is preferably 10% by mass or less, more preferably 0.001% by mass to 5% by mass, and more preferably 0.01% by mass with respect to the total mass of the aqueous solution. % To 3% by mass.
  • the surface tension of an aqueous solution in which a water-soluble organic solvent or a surfactant is mixed is preferably 50 mN / m or less, and more preferably 10 mN / m, from the viewpoint of suppressing uneven peeling due to droplets remaining on the substrate surface and improving the removability.
  • the washing time in the washing step is not particularly limited, and it is preferable to wash the substrate, for example, for 10 seconds to 300 seconds.
  • an air blow is used, and an air blow pressure (preferably 0.1 kg / cm 2) is used. (About 5 kg / cm 2 ) may be appropriately adjusted for drying.
  • the method for manufacturing a circuit wiring according to the present disclosure includes a step of exposing the entire surface of the positive photosensitive resin layer after the etching step (hereinafter, may be referred to as an “entire exposure step”) and a step of exposing the entire positive photosensitive resin layer. And a step of removing the photosensitive resin layer (hereinafter, sometimes referred to as a “removing step”).
  • a step of removing the photosensitive resin layer hereinafter, sometimes referred to as a “removing step”.
  • the etching mask removing property may gradually decrease.
  • a circuit wiring is manufactured by repeatedly applying the method for manufacturing a circuit wiring to a substrate having a base material and a plurality of conductive layers including a first conductive layer and a second conductive layer having different constituent materials. You can also.
  • the method for producing a circuit wiring includes a step of peeling a protective film of the photosensitive transfer material, and an outermost layer of the photosensitive transfer material having a positive photosensitive resin layer with respect to the temporary support.
  • At least the first conductive layer and the conductive layer A first etching step of etching the second conductive layer, a second exposure step of pattern-exposing the first pattern after the first etching step with a pattern different from the first pattern, and a second exposure step
  • a second etching step a step of exposing the entire surface of the second pattern (hereinafter, may be referred to as an “entire exposure step”), and a step of removing the second pattern (hereinafter, referred to as a “removing step”). ) are preferably included in this order.
  • WO 2006/190405 can be referred to, and the contents thereof are incorporated herein.
  • the first pattern 14A remaining on the first conductive layer is exposed to at least a portion corresponding to a portion of the first conductive layer to be removed in a second developing step described later.
  • the same method as the pattern exposure in the above-described exposure step can be applied except that a mask 40 having a different pattern from the mask 30 used in the first exposure step is used.
  • FIG. 1 An example of the second developing step is schematically shown in FIG.
  • the first pattern 14A after the second exposure step is developed to form a second pattern 14B.
  • the second development step the same method as the development in the development step described above can be applied.
  • the same method as the etching in the above-described etching step can be applied, except that an etching solution corresponding to the conductive layer to be removed by etching is selected.
  • the second etching step it is preferable to selectively etch less conductive layers in accordance with a desired pattern than in the above-described etching step.
  • the first conductive layer 24B is etched by using an etchant that selectively etches only the first conductive layer 24B in a region where the photosensitive resin layer is not disposed. May be different from the pattern of the second conductive layer.
  • a circuit wiring including at least two types of conductive layers 24B and 26A is formed.
  • the light source used for the exposure in the entire surface exposure step is not particularly limited, and a known exposure light source can be used.
  • ⁇ ⁇ From the viewpoint of removability, it is preferable to use a light source containing light having the same wavelength as in the above-mentioned exposure step.
  • the exposure amount in the overall exposure step is preferably 5mJ / cm 2 ⁇ 1,000mJ / cm 2, more preferably 10mJ / cm 2 ⁇ 800mJ / cm 2, 100mJ / It is particularly preferred that the density be from cm 2 to 500 mJ / cm 2 .
  • the exposure amount in the entire surface exposure step is preferably equal to or more than the exposure amount in the exposure step, and more preferably greater than the exposure amount in the exposure step.
  • the method of manufacturing a circuit wiring according to the present disclosure includes a step of heating the entire surface exposed positive photosensitive resin layer during the entire surface exposure step, after the exposure step, or both, and before the removal step described below. (Hereinafter, may be referred to as a “heating step”).
  • a heating step By including the heating step, the reaction rate of the photoacid generator and the reaction rate between the generated acid and the positive photosensitive resin can be improved, and as a result, the removal performance can be improved.
  • FIG. 10 An example of the removing step is schematically shown in FIG. After the end of the second etching step, the second pattern 14B remains on a part of the first conductive layer 24B. What is necessary is just to remove the remaining second pattern 14B which is the positive photosensitive resin layer.
  • the removal in the removing step includes, for example, dissolving and dispersing the positive photosensitive resin layer in a removing liquid.
  • the method of removing the remaining positive-type photosensitive resin layer is not particularly limited, but a method of removing by a chemical treatment can be mentioned, and the use of a removing liquid is particularly preferable.
  • a method for removing the positive type photosensitive resin layer the substrate having the photosensitive resin layer or the like in the removal solution with stirring at preferably 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C., is used for 1 minute to 30 minutes.
  • An immersion method may be used.
  • a removal liquid containing 30% by mass or more of water more preferably use a removal solution containing 50% by mass or more of water, and contain 70% by mass or more of water. It is more preferable to use a removing liquid that performs the removal.
  • the removing solution is preferably a removing solution containing an inorganic alkali component and / or an organic alkali component. Examples of the inorganic alkali component include sodium hydroxide, potassium hydroxide, magnesium hydroxide, aluminum hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonia and the like.
  • Examples of the organic alkali component include a primary amine compound, a secondary amine compound, a tertiary amine compound, a quaternary ammonium salt compound, and the like. Specifically, tetramethylammonium hydroxide, diethylamine, Examples include triethylamine, alkanolamine (eg, monomethylethanolamine, dimethylethanolamine, monoethanolamine, 2-amino-2-methyl-1-propanol, etc.), and aromatic amine (eg, pyridine, quinoline, etc.). Above all, from the viewpoint of removability, a removal solution containing an organic alkali component is more preferred, and a removal solution containing an amine compound is particularly preferred. The content of the alkali component may be appropriately selected from the viewpoint of the basic strength and solubility of the alkali component. %, More preferably 0.1 to 10% by mass.
  • the removal liquid preferably contains an organic solvent.
  • organic solvent include esters such as ethyl acetate and ethyl lactate, ketones such as acetone, alcohols such as methanol, ethanol, diacetone alcohol and ethylene glycol, amides such as dimethylformamide and dimethylacetamide, methyl cellosolve, and propylene.
  • Preferred examples include glycol ethers such as glycol methyl ether, tetrahydrofuran, ⁇ -butyrolactone, acetonitrile, dioxane, dimethyl sulfoxide, N-methylpyrrolidone, and the like.
  • a method of removing the positive photosensitive resin by a spray method, a shower method, a paddle method, or the like using a removing liquid is preferable.
  • the method for manufacturing a circuit wiring according to the present disclosure may include other arbitrary steps. For example, the following steps may be mentioned, but it is not limited to these steps.
  • the method may further include a step of attaching a light-transmissive protective film (not shown) on the first pattern.
  • a light-transmissive protective film (not shown)
  • the first pattern is subjected to pattern exposure through the protective film, and after the second exposure step, the protective film is removed from the first pattern, and then the second development step is performed.
  • the method for manufacturing a circuit wiring according to the present disclosure can include a step of performing a process of reducing visible light reflectance of a part or all of a plurality of conductive layers on a base material.
  • An example of the treatment for lowering the visible light reflectance includes an oxidation treatment. For example, by oxidizing copper to form copper oxide, blackening can reduce visible light reflectance.
  • Preferred embodiments of the process for reducing the visible light reflectance are described in paragraphs 0017 to 0025 of JP-A-2014-150118 and paragraphs 0041, 0042, 0048, and 0058 of JP-A-2013-206315. And the contents of this publication are incorporated herein.
  • the method for manufacturing a circuit wiring according to the present disclosure preferably also includes a step of forming an insulating film on the formed circuit wiring and a step of forming a new conductive layer on the insulating film.
  • the above-described second electrode pattern can be formed while being insulated from the first electrode pattern.
  • an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
  • a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
  • the method for manufacturing circuit wiring according to the present disclosure is preferably performed by a roll-to-roll method.
  • the roll-to-roll method uses a substrate that can be wound and unwound as a substrate, and unwinds the substrate or a structure including the substrate before any of the steps included in the circuit wiring manufacturing method ( Hereinafter, it may be referred to as a “unwinding step”), and after any of the steps, a step of winding up a structure including a substrate or a substrate (hereinafter, sometimes referred to as a “winding step”). And a method in which at least one step (preferably all steps or all steps other than the heating step) is performed while transporting a structure including a base material or a substrate.
  • the unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and a known method may be used in a manufacturing method using a roll-to-roll method.
  • FIG. 2 shows a case in which circuit wiring having two different patterns is formed on a circuit wiring forming substrate having two conductive layers, but a substrate to which the circuit wiring manufacturing method according to the present disclosure is applied. Is not limited to two layers.
  • a substrate for circuit wiring formation in which three or more conductive layers are stacked and performing the above-described combination of the exposure step, the developing step, and the etching step three or more times, the three or more conductive layers are respectively different circuit wiring patterns. Can also be formed.
  • the method for manufacturing a circuit wiring uses a substrate having a plurality of conductive layers on both surfaces of a base material, respectively, and a conductive layer formed on both surfaces of the base material. It is also preferable to form circuits sequentially or simultaneously. With such a configuration, it is possible to form a circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the base material and the second conductive pattern is formed on the other surface. In addition, it is also preferable that the circuit wiring for a touch panel having such a configuration is formed on both sides of the base material by roll-to-roll.
  • the circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present disclosure can be applied to various devices.
  • Examples of the device provided with the circuit wiring manufactured by the method for manufacturing a circuit wiring according to the present disclosure include an input device and the like, and a capacitance touch panel is preferable.
  • the input device can be applied to a display device such as an organic EL display device and a liquid crystal display device.
  • the method for manufacturing a touch panel according to the present disclosure includes a step of peeling off the protective film of the photosensitive transfer material (hereinafter, may be referred to as a “peeling step”), and a step of removing the photosensitive transfer material from the temporary support. Bonding the outermost layer on the side having the positive photosensitive resin layer to the substrate having the conductive layer (hereinafter, sometimes referred to as a “bonding step”); and the photosensitive transfer after the bonding step.
  • a step of pattern-exposing the positive photosensitive resin layer of the material hereinafter, may be referred to as an “exposure step”), and developing the positive photosensitive resin layer after the pattern exposure step to form a resin pattern.
  • a step of forming (hereinafter, sometimes referred to as a “development step”) and a step of etching a substrate in a region where the resin pattern is not arranged (hereinafter, referred to as an “etching step”). Including, that there.) I am.
  • a step of forming hereinafter, sometimes referred to as a “development step”
  • etching step a step of etching a substrate in a region where the resin pattern is not arranged
  • a touch panel according to the present disclosure is a touch panel having at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure. Further, 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 detection method in the touch panel according to the present disclosure may be any of known methods such as a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the capacitance type is preferable.
  • the touch panel type a so-called in-cell type (for example, those described in JP-A-2012-517051 shown in FIGS.
  • the method for producing a resin pattern according to the present disclosure includes a step of peeling the protective film of the photosensitive transfer material (hereinafter, may be referred to as a “peeling step”) and a step of removing the protective film of the photosensitive transfer material from the temporary support.
  • peeling step a step of peeling the protective film of the photosensitive transfer material
  • bonding step a step of bonding the outermost layer on the side having the positive photosensitive resin layer to the substrate.
  • a step of pattern-exposing the positive photosensitive resin layer (hereinafter sometimes referred to as an “exposure step”), and a step of developing the positive photosensitive resin layer after the pattern exposure step to form a resin pattern (Hereinafter, may be referred to as “developing step”).
  • exposure step a step of pattern-exposing the positive photosensitive resin layer
  • developing step a step of developing the positive photosensitive resin layer after the pattern exposure step to form a resin pattern
  • the substrate in the method for manufacturing a resin pattern according to the present disclosure may be a substrate itself such as glass, silicon, or a film, or a substrate such as glass, silicon, or a film, and if necessary, a conductive layer. May be a substrate on which an arbitrary layer is formed.
  • the film according to the present disclosure is a biaxially stretched polyethylene terephthalate film in which a uniaxially stretched polyethylene terephthalate film, which is a stretched product in the first stretching direction, is stretched along a film surface in a second stretching direction orthogonal to the first stretching direction. And an undercoat layer which is a stretched product of the coating layer formed on one surface of the uniaxially stretched polyethylene terephthalate film in the second stretching direction.
  • the surface of the undercoat layer has the following (A) and (B) Meet).
  • A) The water contact angle is 75 ° or more.
  • the surface roughness Ra is 45 nm or less.
  • the film according to the present disclosure satisfies the above conditions (A) and (B), the surface energy of the film surface can be reduced and the unevenness can be reduced. Transfer of unevenness can be reduced.
  • the film according to the present disclosure has a biaxially stretched polyethylene terephthalate film and an undercoat layer that is a stretched product, and by further reducing the surface energy of the film, the peelability of the film can be further improved.
  • the surface smoothness and the adhesion between the biaxially oriented polyethylene terephthalate film and the undercoat layer can also be improved.
  • the biaxially stretched polyethylene terephthalate film in the film according to the present disclosure refers to a polyethylene terephthalate film having one surface having a surface roughness Ra of 45 nm or less measured by the method described above.
  • the undercoat layer in the film according to the present disclosure is synonymous with the undercoat layer which is a stretched product described in the section “undercoat layer”.
  • a preferred embodiment of the film according to the present disclosure is the same as the preferred embodiment of the protective film described in the section of “Photosensitive Transfer Material” above.
  • a film according to the present disclosure has a first resin layer and a second resin layer provided on the first resin layer, and the first resin layer is made of polyester. And the surface of the second resin layer satisfies the following (A) and (B).
  • the water contact angle is 75 ° or more.
  • the surface roughness Ra is 45 nm or less.
  • the film according to the present disclosure satisfies the above conditions (A) and (B), the surface energy of the film surface can be reduced and the unevenness can be reduced. Transfer of unevenness can be reduced.
  • the first resin layer contains polyester, and may contain other components as needed.
  • the polyester is preferably polyethylene terephthalate from the viewpoint of smoothness.
  • the thickness of the first resin layer is preferably from 5 ⁇ m to 200 ⁇ m, more preferably from 10 ⁇ m to 150 ⁇ m, further preferably from 10 ⁇ m to 100 ⁇ m, particularly preferably from 10 ⁇ m to 50 ⁇ m.
  • the resin contained in the second resin layer is not particularly limited, and examples thereof include polyolefin, acrylic polymer, and polyester.
  • the second resin layer preferably contains a modified resin from the viewpoint of releasability and reduction of pattern failure, and contains at least one resin selected from the group consisting of an acid-modified resin and a silicone-modified resin. Is more preferred.
  • the second resin layer preferably contains at least one resin selected from the group consisting of a modified polyolefin and a modified acrylic polymer, from the viewpoint of peelability and reduction of pattern failure, It is more preferable to contain at least one resin selected from the group consisting of a modified polyolefin and a silicone-modified acrylic polymer, and it is particularly preferable to contain an acid-modified polyolefin.
  • Preferred examples of the acid-modified polyolefin are the same as the acid-modified polyolefin described in the section of “Undercoat layer”.
  • the resin contained in the second resin layer may be used alone or in combination of two or more.
  • the thickness of the second resin layer is not limited, and is preferably from 10 nm to 550 nm, more preferably from 10 nm to 500 nm, and more preferably from 10 nm to 100 nm, from the viewpoints of peelability and reduction in pattern failure. More preferably, it is particularly preferably from 10 nm to 60 nm.
  • the method for producing a film according to the present disclosure is not particularly limited as long as the second resin layer can be provided on the first resin layer.
  • the second resin layer may be provided on the first resin layer by a coating method, and the first resin layer and the second resin layer may be provided by a co-extrusion method.
  • a first resin layer is formed by film forming, and then a coating liquid for forming a second resin layer is applied on the first resin layer, and a biaxial stretching process is performed. May be performed.
  • a first resin layer is formed by film forming, and after performing a uniaxial stretching treatment, a coating liquid for forming a second resin layer is applied. A method of performing another uniaxial stretching treatment may be used.
  • the method for producing a film according to the present disclosure is a method in which a first resin layer is formed by film forming, a biaxial stretching process is performed, and then a coating liquid for forming a second resin layer is applied. There may be.
  • the method for producing a film according to the present disclosure is a method in which a raw material for forming a first resin layer and a raw material for forming a second resin layer are co-extruded and then biaxially stretched. It may be. Note that the stretching process may be omitted as appropriate.
  • the film according to the present disclosure can protect the surface of an object by being attached to various objects. That is, the protective film is preferably used.
  • the film according to the present disclosure is excellent in releasability, and can reduce the transfer of unevenness to the adherend surface, for example, a member that needs to avoid deformation of the surface shape (for example, a member having high smoothness, And a member having a characteristic surface shape).
  • the protective film according to the present disclosure is more preferably used for protecting various photosensitive transfer materials (dry film resists), and for protecting a photosensitive transfer material having a positive photosensitive resin layer. It is particularly preferred that they be used.
  • Undercoat Layer-Forming Coating Solution 1 The following components were mixed together to obtain a coating liquid 1 for forming an undercoat layer.
  • the obtained coating solution 1 for forming an undercoat layer was subjected to filtration with a 6 ⁇ m filter (F20, manufactured by Mare Filter Systems Co., Ltd.) and membrane deaeration (2 ⁇ 6 radial flow superphobic, manufactured by Polypore).
  • the obtained film roll was used as the protective film of Production Example 1.
  • the substrate of the obtained protective film has a haze of 0.2, and has a heat shrinkage of 1.0% in MD (Machine Direction) and 0 in TD (Transverse Direction) when heated at 150 ° C. for 30 minutes. 0.2%.
  • the thickness of the undercoat layer measured from a cross-sectional TEM (Transmission Electron Microscope) photograph was 50 nm.
  • Production Example 9 A protective film of Production Example 9 was obtained in the same manner as in Production Example 1, except that the coating liquid for forming an undercoat layer was not applied.
  • ⁇ Production Example 10> In the coating step, the following coating liquid for forming an overcoat layer is further coated on the surface of the longitudinally stretched film opposite to the surface to which the coating liquid 1 for forming an undercoat layer is applied so that the thickness after film formation is 60 nm. Except for the application, a protective film of Production Example 10 was obtained in the same manner as in Production Example 1.
  • Acrylic polymer (AS-563A, manufactured by Daicel Finechem Co., Ltd., solid content: 27.5% by mass): 16.7 partsNonionic surfactant (Naroacty CL95, manufactured by Sanyo Chemical Industry Co., Ltd., solid content: 100) % By mass): 0.07 parts
  • Anionic surfactant (Lapisol A-90, manufactured by NOF CORPORATION, solid content: 1% by mass in water): 11.44 parts Carnauba wax dispersion (Cerosol 524, Chukyo) 0.7 parts of a carbodiimide compound (Carbodilite V-02-L2, manufactured by Nisshinbo Industries, diluting with a solid content of 10% by weight in water): 2.09 parts Snowtex XL, manufactured by Nissan Chemical Co., Ltd., solid content: 40% by mass): 0.28 parts, water: 69.0 parts
  • ATHF 2-tetrahydrofuranyl acrylate (synthetic product)
  • MMA Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • EA ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • CHA cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • PMPMA 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • PGMEA propylene glycol monomethyl ether acetate
  • V-601 dimethyl 2,2'-azobis (2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • Photosensitive resin composition 1 was prepared according to the following formulation.
  • -Polymer A1 93.9 parts-Photoacid generator (B-1 below): 2.0 parts-Surfactant (C-1 below): 0.1 parts-Additive (D-1 below): 0.2 parts ⁇ PGMEA: 900 parts
  • the photosensitive resin composition 1 was applied on a 25 ⁇ m-thick polyethylene terephthalate film serving as a temporary support using a slit-shaped nozzle so that the dry film thickness became 3.0 ⁇ m. After drying for 2 minutes in a convection oven at 100 ° C., the undercoat layer side of the protective film of Production Example 1 was brought into contact with the photosensitive resin composition layer and pressure-bonded to produce a photosensitive transfer material. The obtained photosensitive transfer material was used as the photosensitive transfer material of Example 1.
  • Examples 2 to 4, 7 to 11 The photosensitive transfer materials of Examples 2 to 4 and 7 to 11 were produced in the same manner as in Example 1 except that the protective film was changed as described in Table 2.
  • composition 1 for an intermediate layer was prepared according to the following formulation. -Distilled water: 137.0 parts-Methanol: 319.0 parts-NISSO HPC-SSL (manufactured by Nippon Soda Co., Ltd.): 20.6 parts-Snowtex O (manufactured by Nissan Chemical Industries, Ltd.): 68.5 Department
  • the composition 1 for an intermediate layer is slit-coated on a 25 ⁇ m-thick polyethylene terephthalate film serving as a temporary support so as to have a dry film thickness of 2.0 ⁇ m, and then dried in a convection oven at 100 ° C. for 2 minutes. Thus, a water-soluble resin layer serving as an intermediate layer was formed.
  • the photosensitive resin composition 1 was applied onto the water-soluble resin layer using a slit-shaped nozzle so that the dry film thickness became 3.0 ⁇ m. After drying in a convection oven at 100 ° C. for 2 minutes, the protective film of Production Example 3 was pressed to produce a photosensitive transfer material. The obtained photosensitive transfer material was used as the photosensitive transfer material of Example 5.
  • Example 6 A photosensitive transfer material of Example 6 was produced in the same manner as in Example 3, except that the following photosensitive resin composition 2 was used instead of the photosensitive resin composition 1.
  • Comparative Example 1 A photosensitive transfer material of Comparative Example 1 was obtained in the same manner as in Example 1, except that the film of Production Example 8 was used instead of the protective film of Production Example 1.
  • Comparative Example 2 A photosensitive transfer material of Comparative Example 2 was obtained in the same manner as in Example 1, except that the film of Production Example 9 was used instead of the protective film of Production Example 1.
  • Comparative Example 3 A photosensitive transfer material of Comparative Example 3 was obtained in the same manner as in Example 1, except that the following film 2 was used instead of the protective film of Production Example 1.
  • the water contact angle was measured using the peeled surface exposed by peeling the protective film from each of the photosensitive transfer materials of Examples 1 to 11 and Comparative Examples 1 to 3 under the following peeling conditions as a measurement surface. Specifically, using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DROPMASTER-501), the contact angle 7 seconds after dropping 2 ⁇ L of purified water on the measurement surface at a temperature of 25 ° C. was measured. It was measured by the drop method. Table 2 shows the measurement results.
  • the photosensitive transfer material was cut out to 4.5 cm wide by 9 cm long, and the surface on the temporary support side was bonded to a glass plate with a double-sided adhesive tape.
  • An adhesive tape cut to 4.5 cm wide and 15 cm long is attached to the pasted photosensitive transfer material, the width direction of the adhesive tape is aligned with the width direction of the photosensitive transfer material, and the adhesive tape protrudes in the width direction. Instead, the pieces were bonded so that the adhesive tape protruded by 3 cm before and after the length direction.
  • One end of the tape was gripped, and 180 ° peeling was performed at a peeling speed of 500 mm / min using a tensile tester.
  • the pressure-sensitive adhesive tape and the double-sided pressure-sensitive adhesive tape used are those described in JIS Z 0109: 2015, and the tensile tester is a tensile tester (tester grade 1: relative indication error) specified in JIS B 7721: 2009. ⁇ 1.0%) or equivalent tensile tester.
  • ⁇ Measurement of surface roughness Ra> A three-dimensional optical profiler (New View 7300, manufactured by Zygo) was used for the peeled surface exposed by peeling the protective film from each of the photosensitive transfer materials of Examples 1 to 11 and Comparative Examples 1 to 3 under the above peel conditions.
  • the surface profile of the protective film was obtained under the following conditions.
  • the measurement and analysis software uses MicroScope Application 8.3.2. Next, a Surface Map screen is displayed by the analysis software (MetroPro 8.3.2-Microscope Application), and histogram data is obtained in the Surface Map screen. The arithmetic average roughness was calculated from the obtained histogram data, and was defined as an Ra value. Table 2 shows the measurement results.
  • a polyethylene terephthalate (PET) substrate with a copper layer (hereinafter, referred to as a “PET substrate with a copper layer”) in which a copper layer was formed on a 188 ⁇ m-thick PET film with a thickness of 500 nm by a sputtering method. .)It was used.
  • PET substrate with a copper layer a polyethylene terephthalate (PET) substrate with a copper layer
  • a copper layer in which a copper layer was formed on a 188 ⁇ m-thick PET film with a thickness of 500 nm by a sputtering method. .)It was used.
  • the protective film of each photosensitive transfer material was peeled off and the copper Lamination was performed on a layered PET substrate under the conditions of 100 ° C., 2 m / min, and 0.6 MPa to produce a laminate in which a positive resist layer was laminated on a copper layer.
  • the laminated body was exposed to a contact pattern using a photomask provided with a line and space wiring pattern having a line width of 10 ⁇ m (the width ratio of the opening portion to the light shielding portion was 1: 1) without peeling the temporary support. went.
  • a high-pressure mercury lamp using i-ray (365 nm) as a main exposure wavelength was used for exposure.
  • the photosensitive transfer materials of Examples 1 to 11 have good cover releasability, and the patterns manufactured using these photosensitive transfer materials have reduced pattern failure and excellent pattern shape. I understand. Compared with the photosensitive transfer materials of Examples 1 and 2, the photosensitive transfer material of Example 3 has a good pattern without undercut since the acid group contained in the acid-modified polyolefin is a sodium salt. Obtained.
  • ⁇ Photoacid generator> B-1 Compound having the structure shown below (the compound described in paragraph 0227 of JP-A-2013-047765, which was synthesized according to the method described in paragraph 0204).
  • Film 1 Polypropylene film Torayfan 25KW37 (manufactured by Toray Industries, Inc.)
  • Film 2 Polypropylene film Alphan E-501 (manufactured by Oji F-Tex Corporation)
  • Example 101 On a PET substrate having a thickness of 100 ⁇ m, ITO was formed as a second conductive layer by sputtering to a thickness of 150 nm, and copper was formed thereon as a first conductive layer to a thickness of 200 nm by vacuum evaporation. Thus, a circuit forming substrate was obtained.
  • the photosensitive transfer material 1 obtained in Example 1 was laminated on the copper layer (roll temperature: 120 ° C., linear pressure: 0.8 MPa, linear velocity: 1.0 m / min.).
  • Contact pattern exposure was performed using a photomask provided with a pattern A shown in FIG. 3 having a configuration in which conductive layer pads were connected in one direction without removing the temporary support. In the pattern A shown in FIG.
  • a solid line portion SL and a gray portion G are light shielding portions, and a dotted line portion DL is a virtual frame for alignment.
  • the temporary support was peeled off, developed and washed with water to obtain a pattern A.
  • the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.) A substrate on which both copper and ITO were drawn in pattern A was obtained.
  • pattern exposure was performed using a photomask provided with an opening of pattern B shown in FIG. 4 in an aligned state, and development and washing were performed. In the pattern B shown in FIG.
  • a gray portion G is a light-shielding portion, and a dotted line portion DL virtually shows a frame for alignment.
  • the copper layer was etched using Cu-02, and the entire surface of the remaining photosensitive resin layer was exposed to light (300 mJ / cm 2 ) using an ultra-high pressure mercury lamp. It was removed using BONDERITE C-AK P123 (manufactured by Co., Ltd.) to obtain a circuit wiring. Observation of the obtained circuit wiring with a microscope revealed no peeling or chipping and a beautiful pattern.
  • Example 102 On a PET substrate having a thickness of 100 ⁇ m, ITO was formed as a second conductive layer by sputtering to a thickness of 150 nm, and copper was formed thereon as a first conductive layer to a thickness of 200 nm by vacuum evaporation. Thus, a circuit forming substrate was obtained.
  • the photosensitive transfer material 1 obtained in Example 1 was laminated on the copper layer (roll temperature: 120 ° C., linear pressure: 0.8 MPa, linear velocity: 1.0 m / min.). Pattern exposure was performed using a photomask provided with a pattern A shown in FIG. 3 having a configuration in which conductive layer pads were connected in one direction without removing the temporary support.
  • the temporary support was peeled off, developed and washed with water to obtain a pattern A.
  • the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.) A substrate on which both copper and ITO were drawn in pattern A was obtained.
  • PET (A) was laminated as a protective layer on the remaining resist. In this state, pattern exposure was performed using a photomask provided with an opening for pattern B shown in FIG. 4 in an aligned state, and PET (A) was peeled off, followed by development and washing with water.
  • the copper wiring was etched using Cu-02, the entire surface of the remaining photosensitive resin layer was exposed to light (300 mJ / cm 2 ) using an ultra-high pressure mercury lamp, and after being exposed to light for 10 seconds, the removal solution (Henkel ( It was removed using BONDERITE C-AK P123 (manufactured by Co., Ltd.) to obtain a circuit wiring. Observation of the obtained circuit wiring with a microscope revealed no peeling or chipping and a beautiful pattern.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un matériau de transfert photosensible qui comprend séquentiellement et dans l'ordre suivant un support temporaire, une couche de résine photosensible positive et un film protecteur, une surface du film protecteur satisfaisant les exigences (A) et (B) décrites ci-dessous, ladite surface étant en contact avec la couche de résine photosensible positive ; et une application de ce matériau de transfert photosensible. (A) L'angle de contact avec l'eau est de 75° ou plus. (B) La rugosité de surface (Ra) est de 45 nm ou moins.
PCT/JP2019/035363 2018-09-12 2019-09-09 Matériau de transfert photosensible, procédé de production de ligne de câblage de circuit, procédé de production de panneau tactile, procédé de production de motif de résine, et film WO2020054660A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2020546006A JP7065991B2 (ja) 2018-09-12 2019-09-09 感光性転写材料、回路配線の製造方法、タッチパネルの製造方法、樹脂パターンの製造方法、及びフィルム
CN201980048920.1A CN112470074A (zh) 2018-09-12 2019-09-09 感光性转印材料、电路布线的制造方法、触摸面板的制造方法、树脂图案的制造方法及薄膜

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2018170973 2018-09-12
JP2018-170973 2018-09-12
JP2019-057423 2019-03-25
JP2019057423 2019-03-25

Publications (1)

Publication Number Publication Date
WO2020054660A1 true WO2020054660A1 (fr) 2020-03-19

Family

ID=69778084

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/035363 WO2020054660A1 (fr) 2018-09-12 2019-09-09 Matériau de transfert photosensible, procédé de production de ligne de câblage de circuit, procédé de production de panneau tactile, procédé de production de motif de résine, et film

Country Status (4)

Country Link
JP (1) JP7065991B2 (fr)
CN (1) CN112470074A (fr)
TW (1) TW202017748A (fr)
WO (1) WO2020054660A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022054374A1 (fr) * 2020-09-14 2022-03-17
WO2022054599A1 (fr) * 2020-09-14 2022-03-17 富士フイルム株式会社 Matériau de transfert photosensible, procédé de fabrication de motif de résine et procédé de fabrication de dispositif électronique
WO2022138493A1 (fr) * 2020-12-25 2022-06-30 富士フイルム株式会社 Procédé de fabrication de stratifié, procédé de fabrication de câblage de circuit, et film de transfert

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008302547A (ja) * 2007-06-06 2008-12-18 Mitsubishi Plastics Inc 感光性粘着樹脂用保護ポリエステルフィルム
JP2014085643A (ja) * 2012-10-26 2014-05-12 Fujifilm Corp 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
WO2014175274A1 (fr) * 2013-04-24 2014-10-30 日立化成株式会社 Élément photosensible, rouleau d'élément photosensible, procédé de production de motif de réserve, et composant électronique
JP2015183117A (ja) * 2014-03-25 2015-10-22 富士フイルム株式会社 透明フィルム及びその製造方法、積層フィルム、透明導電フィルム、ハードコートフィルム、タッチパネル、偏光板ならびに表示装置
JP2016210066A (ja) * 2015-05-07 2016-12-15 三菱樹脂株式会社 積層ポリエステルフィルム

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010045151A (ko) * 1999-11-03 2001-06-05 구광시 드라이필름 포토레지스트
JP2009080194A (ja) * 2007-09-25 2009-04-16 Fujifilm Corp 重合性樹脂組成物、転写材料、カラーフィルタ及びその製造方法、液晶表示装置用スペーサ及びその製造方法、並びに液晶表示装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008302547A (ja) * 2007-06-06 2008-12-18 Mitsubishi Plastics Inc 感光性粘着樹脂用保護ポリエステルフィルム
JP2014085643A (ja) * 2012-10-26 2014-05-12 Fujifilm Corp 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
WO2014175274A1 (fr) * 2013-04-24 2014-10-30 日立化成株式会社 Élément photosensible, rouleau d'élément photosensible, procédé de production de motif de réserve, et composant électronique
JP2015183117A (ja) * 2014-03-25 2015-10-22 富士フイルム株式会社 透明フィルム及びその製造方法、積層フィルム、透明導電フィルム、ハードコートフィルム、タッチパネル、偏光板ならびに表示装置
JP2016210066A (ja) * 2015-05-07 2016-12-15 三菱樹脂株式会社 積層ポリエステルフィルム

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022054374A1 (fr) * 2020-09-14 2022-03-17
WO2022054374A1 (fr) * 2020-09-14 2022-03-17 富士フイルム株式会社 Matériau de transfert photosensible, procédé de production d'un motif de résine, procédé de production d'un câblage de circuit et procédé de production d'un dispositif électronique
WO2022054599A1 (fr) * 2020-09-14 2022-03-17 富士フイルム株式会社 Matériau de transfert photosensible, procédé de fabrication de motif de résine et procédé de fabrication de dispositif électronique
WO2022138493A1 (fr) * 2020-12-25 2022-06-30 富士フイルム株式会社 Procédé de fabrication de stratifié, procédé de fabrication de câblage de circuit, et film de transfert

Also Published As

Publication number Publication date
TW202017748A (zh) 2020-05-16
JP7065991B2 (ja) 2022-05-12
JPWO2020054660A1 (ja) 2021-05-20
CN112470074A (zh) 2021-03-09

Similar Documents

Publication Publication Date Title
JP6100500B2 (ja) 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
WO2020054660A1 (fr) Matériau de transfert photosensible, procédé de production de ligne de câblage de circuit, procédé de production de panneau tactile, procédé de production de motif de résine, et film
CN107132731B (zh) 感光性转印材料及电路布线的制造方法
TW201922815A (zh) 電路配線的製造方法、觸控面板的製造方法及附圖案基材的製造方法
TW201924935A (zh) 感光性轉印材料、樹脂圖案製造方法、及配線製造方法
TW201921108A (zh) 感光性轉印材料、電路配線的製造方法及觸控面板的製造方法
TW201912667A (zh) 感光性轉印材料及其製造方法、以及電路配線的製造方法
JP6821046B2 (ja) 回路配線の製造方法及びタッチパネルの製造方法
WO2020158316A1 (fr) Matériau de transfert photosensible, procédé de production de motif en résine, procédé de production de câblage de circuit, procédé de production d'écran tactile, et film et procédé de production associés
WO2018179641A1 (fr) Matériau de transfert photosensible et procédé de production de câblage de circuit
JP6992097B2 (ja) レジストパターンの製造方法、回路基板の製造方法及びタッチパネルの製造方法
JP6685461B2 (ja) 感光性転写材料、回路配線の製造方法及びタッチパネルの製造方法
WO2020116068A1 (fr) Matériau de transfert, procédé de production d'un motif en résine, procédé de production d'un câblage de circuit, et procédé de fabrication d'un panneau tactile
WO2019225362A1 (fr) Matériau de transfert photosensible, procédé de fabrication de motif de résine, procédé de fabrication de câblage de circuit et procédé de fabrication de panneau tactile
JP6830398B2 (ja) 感光性転写材料用重合体溶液の製造方法、感光性転写材料用組成物の製造方法、感光性転写材料の製造方法、回路配線の製造方法、タッチパネルの製造方法、感光性転写材料用重合体溶液の製造に用いられる組成物、感光性転写材料用重合体溶液、感光性転写材料用組成物及び感光性転写材料
WO2019077924A1 (fr) Procédé de production d'une carte de circuit imprimé et procédé de production d'un écran tactile
JP6685460B2 (ja) 感光性転写材料、回路配線の製造方法及びタッチパネルの製造方法
WO2019021622A1 (fr) Composition de résine photosensible, matériau de transfert photosensible, procédé de fabrication de câblage de circuit et procédé de fabrication de panneau tactile
WO2019225363A1 (fr) Matériau de transfert photosensible, procédé de production de motif de résine, procédé de fabrication de câblage de circuit, et procédé de fabrication de panneau tactile
JP2019128445A (ja) 感光性転写材料及びその製造方法、樹脂パターンの製造方法、並びに、回路配線の製造方法

Legal Events

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

Ref document number: 19861120

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020546006

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19861120

Country of ref document: EP

Kind code of ref document: A1