WO2019225362A1 - Photosensitive transfer material, method for producing resin pattern, method for manufacturing circuit wiring, and method for manufacturing touch panel - Google Patents

Photosensitive transfer material, method for producing resin pattern, method for manufacturing circuit wiring, and method for manufacturing touch panel Download PDF

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Publication number
WO2019225362A1
WO2019225362A1 PCT/JP2019/018814 JP2019018814W WO2019225362A1 WO 2019225362 A1 WO2019225362 A1 WO 2019225362A1 JP 2019018814 W JP2019018814 W JP 2019018814W WO 2019225362 A1 WO2019225362 A1 WO 2019225362A1
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Prior art keywords
group
structural unit
resin layer
photosensitive resin
acid
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PCT/JP2019/018814
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French (fr)
Japanese (ja)
Inventor
知樹 松田
一真 両角
山田　悟
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富士フイルム株式会社
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Priority to CN201980034172.1A priority Critical patent/CN112204467B/en
Priority to JP2020521156A priority patent/JP6968273B2/en
Publication of WO2019225362A1 publication Critical patent/WO2019225362A1/en

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

Definitions

  • the present disclosure relates to a photosensitive transfer material, a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method.
  • a display device such as an organic electroluminescence (EL) display device and a liquid crystal display device
  • a touch panel such as a capacitance type input device
  • an electrode pattern corresponding to a sensor of a visual recognition part a wiring of a peripheral wiring part
  • a lead-out wiring part A conductive layer pattern such as is provided inside the touch panel.
  • a patterned layer is formed by a photosensitive resin composition layer provided on an arbitrary substrate using a photosensitive transfer material because the number of steps for obtaining a required pattern shape is small.
  • a method of developing after exposure through a mask having a desired pattern is widely used.
  • Patent Document 1 what was described in patent document 1 or 2 is known as a conventional photosensitive resin composition.
  • Patent Document 1 a polymer component containing a polymer satisfying at least one of the following (1) and (2), (1) (a-1) an acid group is an acid A polymer having a structural unit having a group protected by a decomposable group, and (a-2) a structural unit having a crosslinkable group, and (2) (a-1) the acid group is protected by an acid-decomposable group.
  • the polymer (S) is a general formula in all repeating units of the polymer (S).
  • the molar ratio of the structural unit represented by (2) is represented by the general formula (1) in all repeating units of the polymer (S). 0.3 to 5 times the molar ratio of structural units, the photosensitive resin composition is disclosed.
  • R 10 and R 11 each independently represent a hydrogen atom or a methyl group
  • L 1 and L 2 each independently represent a single bond or a divalent linkage
  • R 1 to R 4 each independently represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms
  • R 5 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or Represents an alkoxy group having 1 to 12 carbon atoms.
  • Patent Document 2 discloses at least one of repeating unit a having a carboxyl group substituted with an acid labile group and repeating units b1 and b2 having a sulfonium salt represented by the following general formula (1). As described above, a resist material comprising a polymer compound having a repeating unit c having an amino group has been disclosed.
  • R 1 , R 3 , R 8 and R 12 each independently represents a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group.
  • R 2 represents an acid labile group.
  • X represents a single group.
  • R 4 is an alkylene group having 1 to 10 carbon atoms, or 6 to 10 carbon atoms
  • An arylene group which may have a fluorine atom, a trifluoromethyl group, an ester group, an ether group or a lactone ring
  • R 5 , R 6 , R 7 , R 9 , R 10 and R 11 are the same, or It is a different type of linear, branched or cyclic alkyl group having 1 to 12 carbon atoms and may contain a carbonyl group, an ester group or an ether group, or an aryl group having 6 to 12 carbon atoms, or a carbon number 7 ⁇ 20
  • Aralkyl Or a thiophenyl group which may have an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alk
  • R 13 is a single bond, or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms
  • R 14 and R 15 are each independently a hydrogen atom or a linear chain having 1 to 20 carbon atoms.
  • An alkyl group, branched or cyclic alkyl group, t-butoxycarbonyl group, or t-allyloxycarbonyl group, an ether bond, a thioether bond , Hydroxyl group, formyl group, an acetoxy group, a cyano group, may have an aromatic group, and R 13 and R 14, R 13 and R 15, R 14 and R 15 are respectively bonded to form a ring R 16 may be bonded to a hydrogen atom or R 15 to form a ring, Z is a single bond, a methylene group, an arylene group, —O—, —C ( ⁇ O) —O—, or —C ( ⁇ O) —O—R 18 —C ( ⁇ O) —O—, wherein R 18 is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. 0 ⁇ a ⁇ 1.0, 0 ⁇ b1 ⁇ 0.3, 0 ⁇
  • Patent Document 3 includes a temporary support, a polymer having a structural unit represented by the following general formula A and a structural unit having an acid group, and having a glass transition temperature of 90 ° C. or lower, and a photoacid generator. There is disclosed a photosensitive transfer material having a positive photosensitive resin layer containing.
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group. Alternatively, it represents an aryl group, and R 31 or R 32 and R 33 may be linked to form a cyclic ether.
  • R 34 represents a hydrogen atom or a methyl group
  • X 0 represents a single bond or an arylene group.
  • Patent Document 1 Japanese Patent Laid-Open No. 2015-187634
  • Patent Document 2 Japanese Patent Laid-Open No. 2011-39266
  • Patent Document 3 Japanese Patent Laid-Open No. 2017-156735
  • the problem to be solved by an embodiment of the present invention is to provide a photosensitive transfer material having excellent laminating properties and resolution.
  • Another problem to be solved by another embodiment of the present invention is to provide a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method using the photosensitive transfer material. .
  • Means for solving the above problems include the following aspects. ⁇ 1> A temporary support and a photosensitive resin layer, wherein the photosensitive resin layer includes a polymer component satisfying at least one of the following a1 and a2, and a photoacid generator, and the polymer component The photosensitive transfer material whose glass transition temperature is 90 degrees C or less.
  • a1 Polymer component containing a structural unit having an acid group protected by an acid-decomposable group and a polymer having a structural unit having a pKaH group of 3 or more
  • a2 An acid group protected by an acid-decomposable group
  • a polymer component comprising a polymer having a structural unit having a structural unit having a pKaH group of 3 or more ⁇ 2>
  • All pKaH groups contained in the photosensitive resin layer are 3 or more groups Among these, the photosensitive transfer material as described in ⁇ 1> whose ratio of the group whose pKaH is 3 or more contained in the polymer component is 30 mol% or more.
  • the ratio of the group having 3 or more pKaH contained in the polymer component is 50 mol% or more ⁇ 1> or The photosensitive transfer material as described in ⁇ 2>.
  • the polymer in the polymer component further includes a structural unit other than a structural unit having an acid group protected by an acid-decomposable group and a structural unit having a pKaH of 3 or more.
  • ⁇ 1> to ⁇ 3 > The photosensitive transfer material as described in any one of>.
  • ⁇ 5> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 4>, wherein the structural unit having the pKaH group of 3 or more is a structural unit represented by the following formula I or formula II.
  • R 1 represents a hydrogen atom or a methyl group
  • Z is a single bond, a methylene group, an arylene group, —O—, —C ( ⁇ O) —NH—, or —C ( ⁇ O) —.
  • R 2 may have a single bond or at least one group selected from the group consisting of an ether bond, a urethane bond, a urea bond, an amide bond, an ester bond and a carbonate bond.
  • a linear group having 1 to 20 carbon atoms which may have at least one group selected from the group consisting of a group, a urethane bond, a urea bond, an amide bond, an ester bond, a carbonate bond and an aromatic group, Represents a branched or cyclic alkyl group, R 2 and R 3 , R 2 and R 4 , or R 3 and R 4 may be bonded to each other to form a ring, and Q 1 represents a nitrogen atom Represents an aromatic group or a nitrogen-containing heteroaromatic group.
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group or Represents an aryl group, and R 31 or R 32 and R 33 may combine to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or a divalent linking group. Represents.
  • ⁇ 8> A step of bringing the photosensitive resin layer in the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 7> into contact with a substrate and bonding the substrate; and a step of pattern exposing the photosensitive resin layer; And a step of developing the exposed photosensitive resin layer to form a pattern, in this order.
  • ⁇ 9> A step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 7> into contact with a substrate having a conductive layer and bonding the photosensitive resin layer, A circuit wiring including a pattern exposure step, a step of developing the exposed photosensitive resin layer to form a pattern, and a step of etching a conductive layer in a region where the pattern is not disposed. Production method.
  • ⁇ 10> The method for manufacturing a circuit wiring according to ⁇ 9>, wherein the conductive layer is a layer containing copper.
  • ⁇ 11> The step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 7> into contact with a substrate having a conductive layer and bonding the photosensitive resin layer, Manufacturing of a touch panel that includes a pattern exposure step, a step of developing the exposed photosensitive resin layer to form a pattern, and a step of etching a conductive layer in a region where the pattern is not disposed in this order. Method.
  • a photosensitive transfer material that is excellent in laminating suitability and resolution.
  • a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method using the photosensitive transfer material can be provided.
  • FIG. 6 is a schematic diagram showing a pattern A.
  • FIG. 6 is a schematic diagram showing a pattern B.
  • symbol may be abbreviate
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • (meth) acryl” represents both and / or acryl and methacryl
  • (meth) acrylate” represents both and / or acrylate and methacrylate.
  • the amount of each component in the composition is the sum of the plurality of corresponding substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition.
  • the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
  • the notation that does not indicate substitution and non-substitution includes those having no substituent and those having a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “exposure” includes not only exposure using light, but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified.
  • an emission ray spectrum of a mercury lamp an actinic ray (active energy ray) such as a far ultraviolet ray, an extreme ultraviolet ray (EUV light) represented by an excimer laser, an X-ray, and an electron beam is used.
  • actinic ray active energy ray
  • EUV light extreme ultraviolet ray
  • the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
  • “mass%” and “weight%” are synonymous, and “part by mass” and “part by weight” are synonymous.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) unless otherwise specified.
  • the molecular weight was detected by a gel permeation chromatography (GPC) analyzer using a THF (tetrahydrofuran) solvent and a differential refractometer, and converted using polystyrene as a standard substance.
  • GPC gel permeation chromatography
  • a photosensitive transfer material includes a temporary support and a photosensitive resin layer, and the photosensitive resin layer satisfies at least one of the following a1 and a2, and a photoacid generator
  • the glass transition temperature (Tg) of the polymer component is 90 ° C. or lower.
  • a2 An acid group protected by an acid-decomposable group
  • a polymer component comprising a polymer having a structural unit having a pKaH group of 3 or more.
  • the photosensitive transfer material according to the present disclosure is a positive photosensitive transfer material. .
  • Conventional positive photosensitive transfer materials may contain a low molecular weight basic compound (also referred to as “quencher”) for the purpose of capturing the generated acid and stopping the decomposition reaction of the acid-decomposable group. It was. However, in the photosensitive transfer material to which the conventional low molecular weight basic compound is added, the low molecular weight basic compound tends to be unevenly distributed on the transferred substrate side, etc., and the uneven distribution causes tailing at the bottom of the resist pattern during development, The present inventors have found that the resolution may be poor. This problem is specific to a photosensitive transfer material containing an acid-decomposable polymer having a Tg of 90 ° C. or less and a photoacid generator, and has a high Tg of 90 g.
  • a photosensitive transfer material containing an acid-decomposable polymer having a Tg of 90 ° C. or less and a photoacid generator, and has a high Tg of 90 g.
  • the photosensitive transfer material according to the present disclosure has the above-described configuration, so that excessive diffusion of acid generated from the photoacid generator can be suppressed, and a certain amount of time has elapsed after the photosensitive transfer material is exposed. Even when the development is performed after this, it is possible to suppress the thinning of the line width of the obtained resin pattern (also referred to as “retention time-dependent suppression”).
  • FIG. 1 schematically illustrates an example of a layer configuration of a photosensitive transfer material according to the present disclosure.
  • a temporary support 10 a photosensitive resin layer 12, and a cover film 14 are laminated in this order.
  • the photosensitive resin layer 12 includes a polymer component satisfying at least one of the a1 and a2 and a photoacid generator, and the glass transition temperature of the polymer component is 90 ° C. or lower.
  • constituent materials and the like of the photosensitive transfer material according to the present disclosure will be described.
  • the temporary support is a support that supports the photosensitive resin layer and can be peeled off.
  • the temporary support used in the present disclosure preferably has light transparency from the viewpoint that the photosensitive resin layer can be exposed through the temporary support when the photosensitive resin layer is subjected to pattern exposure.
  • having light transmittance means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of light used for pattern exposure is exposure. From the viewpoint of improving sensitivity, 60% or more is preferable, and 70% or more is more preferable.
  • Examples of the method for measuring the transmittance include a method of measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
  • Examples of the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is particularly preferable from the viewpoints of strength and flexibility.
  • Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a biaxially stretched polyethylene terephthalate film is particularly preferable.
  • the thickness of the temporary support is not particularly limited, but is preferably in the range of 5 ⁇ m to 200 ⁇ m, and more preferably in the range of 10 ⁇ m to 150 ⁇ m from the viewpoint of ease of handling and versatility.
  • the thickness of the temporary support is selected according to the material from the viewpoints of strength as a support, flexibility required for bonding with a wiring forming substrate, light transmittance required in the first exposure process, and the like. That's fine.
  • the photosensitive transfer material according to the present disclosure has at least a temporary support and a photosensitive resin layer, and the photosensitive resin layer satisfies at least one of the a1 and a2, and a photoacid generator.
  • the glass transition temperature (Tg) of the polymer component is 90 ° C. or less.
  • the photosensitive resin layer is preferably a chemically amplified positive photosensitive resin layer. Photoacid generators such as onium salts and oxime sulfonate compounds described below are used to deprotect protected acid groups in binders in which the acid generated in response to actinic rays has acid-decomposable and protected acid groups.
  • the acid produced by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as the power of 10 High sensitivity is obtained as a result of so-called chemical amplification.
  • a quinonediazide compound NQD
  • a carboxy group is generated by a sequential photochemical reaction, but its quantum yield is always 1 or less. Not applicable.
  • ⁇ polymer component The polymer component contained in the photosensitive resin layer satisfies at least one of the following a1 and a2. Moreover, the glass transition temperature of the said polymer component is 90 degrees C or less.
  • a1 Polymer component containing a structural unit having an acid group protected by an acid-decomposable group and a polymer having a structural unit having a pKaH group of 3 or more
  • a2 An acid group protected by an acid-decomposable group
  • a polymer component comprising a polymer having a structural unit having pKaH and a structural unit having a structural unit having 3 or more groups
  • the polymer component preferably satisfies the above a1 from the viewpoint of developability, and preferably satisfies the above a2 from the viewpoint of easy physical property adjustment. Further, all the polymers contained in the polymer component are each at least one structural unit selected from the group consisting of a structural unit having an acid group protected with an acid-decomposable group and a structural unit having an acid group. It is preferable that it is a polymer which has. Each of the polymers shown in a1 and a2 may contain only one type or two or more types. Moreover, the polymer component may further contain a polymer other than the polymers shown in the a1 and a2. Unless otherwise specified, the polymer component in the present disclosure means one including other polymers added as necessary in addition to the above-described aspect of a1 or a2.
  • the polymer in the polymer component is preferably an addition polymerization type resin, and is derived from a structural unit derived from (meth) acrylic acid and / or an ester thereof, and / or a styrene compound and / or a vinyl naphthalene compound. It is more preferable that the polymer contains a structural unit, and a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof is more preferable. In addition, you may have structural units other than the above, for example, a structural unit derived from a vinyl compound.
  • the glass transition temperature (Tg) of the polymer component in the present disclosure is 90 ° C. or lower, preferably 60 ° C. or lower, and more preferably 50 ° C. or lower. Within the above range, the photosensitive resin layer has high adhesion and excellent transferability.
  • the lower limit of Tg is not particularly limited, but is preferably ⁇ 20 ° C. or higher, more preferably ⁇ 10 ° C. or higher, still more preferably 10 ° C. or higher, and particularly preferably 25 ° C. or higher. When the Tg of the polymer component is ⁇ 20 ° C.
  • the glass transition temperature (Tg) of the polymer having a unit or the polymer having a structural unit having a pKaH group of 3 or more is preferably 90 ° C. or less independently from the viewpoint of transferability. It is more preferably 20 ° C. or higher and 70 ° C. or lower, further preferably 10 ° C. or higher and 60 ° C. or lower, and particularly preferably 25 ° C. or higher and 50 ° C. or lower.
  • the glass transition temperature of the polymer can be measured using differential scanning calorimetry (DSC). A specific measuring method is performed in accordance with the method described in JIS K 7121 (1987). As the glass transition temperature in this specification, an extrapolated glass transition start temperature (hereinafter sometimes referred to as Tig) is used. The method for measuring the glass transition temperature will be described more specifically.
  • the heating rate is about 20 ° C./min and about 30 times higher than the temperature at which the glass transition is completed. Heat to a higher temperature and draw a DTA or DSC curve.
  • the extrapolated glass transition start temperature (Tig) that is, the glass transition temperature Tg in the present specification, is a straight line obtained by extending the low-temperature side baseline in the DTA curve or DSC curve to the high-temperature side, and the step-like change portion of the glass transition. Calculated as the temperature of the intersection with the tangent drawn at the point where the slope of the curve is maximum.
  • the FOX formula is used as a guideline. It is possible to control the Tg of the target polymer.
  • Tg of the homopolymer of the first structural unit contained in the polymer is Tg1
  • the mass fraction in the copolymer of the first structural unit is W1
  • the Tg of the homopolymer of the second structural unit Is Tg2 and the mass fraction in the copolymer of the second structural unit is W2
  • the Tg0 (K) of the copolymer containing the first structural unit and the second structural unit is It is possible to estimate according to the equation.
  • FOX formula: 1 / Tg0 (W1 / Tg1) + (W2 / Tg2)
  • a copolymer having a desired Tg can be obtained by adjusting the type and mass fraction of each structural unit contained in the copolymer using the FOX formula described above. It is also possible to adjust the Tg of the polymer by adjusting the weight average molecular weight of the polymer.
  • the glass transition temperature of the polymer component in the present disclosure is obtained by measuring or calculating the glass transition temperature of each polymer contained in the polymer component, and the weighted average, that is, the glass transition temperature of each polymer and the entire polymer component. It shall be obtained by adding the product of the mass ratio to.
  • Tg of polymer component Tg of polymer 1 ⁇ content ratio of polymer 1 + Tg of polymer 2 ⁇ content ratio of polymer 2+...
  • the weight average molecular weight (Mw) of the polymer is preferably 60,000 or less, more preferably 2,000 to 60,000 in terms of polystyrene, from the viewpoint of laminate suitability, More preferably, it is 000 to 50,000, and particularly preferably 15,000 to 50,000.
  • the weight average molecular weight and number average molecular weight of the polymer can be measured by GPC (gel permeation chromatography), and various commercially available apparatuses can be used as the measuring apparatus, and the contents of the apparatus, and Measurement techniques are known to those skilled in the art.
  • HLC registered trademark
  • -8220GPC manufactured by Tosoh Corporation
  • TSKgel registered trademark
  • Super HZM-M 4 .6 mm ID ⁇ 15 cm, manufactured by Tosoh Corporation
  • Super HZ4000 4 mm ID ⁇ 15 cm, manufactured by Tosoh Corporation
  • Super HZ3000 4 mm ID ⁇ 15 cm, manufactured by Tosoh Corporation
  • Super HZ2000 4 mm ID
  • THF tetrahydrofuran
  • Measurement conditions are 0.2% by mass, flow rate is 0.35 ml / min, sample injection amount is 10 ⁇ l, measurement temperature is 40 ° C., and a differential refractive index (RI) detector is used. be able to.
  • the calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “ It can be produced using at least two of any of the seven samples of “A-2500” and “A-1000”.
  • the ratio (dispersion degree) between the number average molecular weight and the weight average molecular weight of the polymer is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.
  • the polymer component includes a polymer having at least a structural unit having a pKaH of 3 or more.
  • a polymer having a structural unit having an acid group protected by an acid-decomposable group and a structural unit having a pKaH group of 3 or more, or an acid protected by an acid-decomposable group examples thereof include a polymer having no structural unit having a group and having a structural unit having a pKaH of 3 or more.
  • pKaH is a pKa of a conjugate acid
  • a group having a pKaH of 3 or more represents a group having a pKa of a conjugate acid of the group of 3 or more.
  • the value of pKaH of —NH 2 is the value of pKa of —NH 3 + .
  • pKaH is a calculated value obtained by ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08). Specifically, from the chemical structure of the structural unit having a specific functional group, the above-mentioned ACD / ChemSketch is used to calculate the pKaH value of the specific functional group.
  • the group having a pKaH of 3 or more is preferably a group having a pKaH of 4 or more, more preferably a group having a pKaH of 5 or more, from the viewpoints of resolution and retention time-dependent suppression.
  • a group of 5 or more and 15 or less is more preferable, and a group having a pKaH of 6 or more and 10 or less is particularly preferable.
  • the polymer component preferably includes a polymer having at least a constituent unit having a pKaH group of 4 or more, and a pKaH of 5 or more, from the viewpoint of resolution and retention time-dependent suppression.
  • a polymer having at least a structural unit having a group it is more preferable to include a polymer having at least a structural unit having a group, and it is further preferable to include a polymer having at least a structural unit having a pKaH of 5 or more and 15 or less, and a group having a pKaH of 6 to 10 or less. It is particularly preferable to include a polymer having at least a structural unit having.
  • the group having a pKaH of 3 or more is preferably a group having a nitrogen atom from the viewpoint of resolution and retention time-dependent suppression, and is an aliphatic amino group, an aromatic amino group, or a nitrogen-containing complex. It is more preferably an aromatic ring group, further preferably an aliphatic amino group or a nitrogen-containing heteroaromatic ring group, and particularly preferably an aliphatic amino group.
  • the aliphatic amino group may be any of a primary amino group, a secondary amino group, or a tertiary amino group, but from the viewpoints of resolution and retention time dependence suppression, It is preferably a secondary amino group or a tertiary amino group.
  • the aromatic amino group is preferably an anilino group, a monoalkylanilino group, or a dialkylanilino group, and more preferably a monoalkylanilino group or a dialkylanilino group.
  • the nitrogen-containing heteroaromatic ring in the nitrogen-containing heteroaromatic group is preferably a pyridine ring, an imidazole ring or a triazole ring, more preferably a pyridine ring or an imidazole ring, and a pyridine ring. Is particularly preferred.
  • the nitrogen-containing heteroaromatic group may further have a substituent on the nitrogen-containing heteroaromatic ring.
  • the substituent is not particularly limited, but is preferably an alkyl group, and more preferably a methyl group.
  • the group having a pKaH of 3 or more is particularly preferably a group having an alkylamine structure from the viewpoint of resolution and retention time-dependent suppression.
  • alkylamine structure include dialkylamine and trialkylamine. Specifically, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, 1,2,2,6,6-penta Examples include an alkyl-4-piperidyl group and a 2,2,6,6-tetraalkyl-4-piperidyl group.
  • the structural unit having a pKaH group of 3 or more is preferably a structural unit represented by the following formula I or formula II from the viewpoints of resolution and retention time-dependent inhibition properties. More preferably, it is a structural unit.
  • R 1 represents a hydrogen atom or a methyl group
  • Z represents a single bond, a methylene group, an arylene group, —O—, —C ( ⁇ O) —NH—, or —C ( ⁇ O) —.
  • R 2 may have a single bond or at least one group selected from the group consisting of an ether bond, a urethane bond, a urea bond, an amide bond, an ester bond and a carbonate bond.
  • a linear group having 1 to 20 carbon atoms which may have at least one group selected from the group consisting of a group, a urethane bond, a urea bond, an amide bond, an ester bond, a carbonate bond, and an aromatic group
  • Q 1 is a nitrogen atom
  • Z in Formula I is a single bond, an arylene group, —C ( ⁇ O) —NH— or —C ( ⁇ O) —O— from the viewpoint of resolution, retention time-dependent inhibition, and ease of synthesis. It is preferably an arylene group, more preferably an —C ( ⁇ O) —NH— or —C ( ⁇ O) —O—, and —C ( ⁇ O) —NH— or —C ( ⁇ O). Particularly preferred is —O—.
  • Z in Formula II is preferably a single bond, an arylene group, or —C ( ⁇ O) —O—, and is a single bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. Is more preferable.
  • R 2 in Formula I has at least one group selected from the group consisting of an ether bond, a urethane bond, and a urea bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. It is preferably a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and has at least one group selected from the group consisting of an ether bond, a urethane bond and a urea bond. It is more preferably a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms, particularly preferably a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms.
  • R 2 in Formula II is preferably a single bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis.
  • R 3 and R 4 in formula I are each independently a hydrogen atom or a carbon number of 1 to 20 which may have an ether bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis.
  • the linear, branched or cyclic alkyl group is preferably a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
  • R 2 , R 3 and R 4 in the formula I are combined to form a nitrogen-containing aliphatic ring is preferable, An embodiment in which a piperidine ring is formed is more preferable.
  • Q 1 in Formula II is preferably a nitrogen-containing heteroaromatic group from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis, and is pyridyl, methylpyridyl, imidazolyl, methylimidazolyl Group or a triazolyl group is more preferable, a pyridyl group is more preferable, and a 4-pyridyl group is particularly preferable.
  • the monomer that forms a structural unit having a pKaH group of 3 or more include the following monomers. 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2- (dimethylamino) ethyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2,2 methacrylate , 6,6-tetramethyl-4-piperidyl, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2- (diethylamino) ethyl methacrylate, 2- (dimethylamino) ethyl acrylate, acrylic acid 2- (diethylamino) ethyl, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate, N- (3-diethylamino) propyl methacrylate, N- (3-diethylamino acrylate)
  • R 12 represents a hydrogen atom or a methyl group.
  • Resin having at least a structural unit having pKaH having 3 or more groups for example, a polymer having a structural unit having an acid group protected with an acid-decomposable group, and a structural unit having pKaH having 3 or more groups,
  • the content of the structural unit having pKaH having 3 or more groups in the polymer having a structural unit having pKaH having 3 or more groups is determined from the viewpoint of resolution and retention time dependence suppression. It is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.05% by mass or more and 20% by mass or less, and more preferably 0.1% by mass or more and 10% by mass or less with respect to the total mass of the coalescence.
  • the content of the structural unit in which the pKaH has a group of 3 or more in the polymerizable component is 0.01% with respect to the total mass of the polymer component from the viewpoint of resolution and retention time-dependent suppression. It is preferably from 10% by mass to 10% by mass, more preferably from 0.05% by mass to 8% by mass, still more preferably from 0.1% by mass to 5% by mass, The content is particularly preferably from 4% by weight to 4% by weight, and most preferably from 0.5% by weight to 2% by weight.
  • the photosensitive resin layer may contain a basic compound having a pKaH group of 3 or more in addition to the pKaH group of 3 or more in the polymer.
  • the ratio of the groups having 3 or more pKaH contained in the polymer component is 30 mol% or more, preferably 50 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more and 100 mol% or less.
  • the content (content ratio: mass ratio) of the structural unit having a pKaH group of 3 or more in the polymer A can be confirmed by the intensity ratio of the peak intensity calculated by 13 C-NMR measurement by a conventional method. .
  • the polymer component includes a polymer having at least a structural unit having an acid group protected with an acid-decomposable group.
  • a polymer having a structural unit having an acid group protected with an acid-decomposable group and a structural unit having pKaH having 3 or more groups, or a structure having pKaH having 3 or more groups examples thereof include a polymer having a constitutional unit having no unit and having an acid group protected with an acid-decomposable group.
  • the “acid group protected with an acid-decomposable group” in the present disclosure may be any known acid group and acid-decomposable group, and is not particularly limited. Specific examples of the acid group preferably include a carboxy group and a phenolic hydroxyl group.
  • the acid group protected with an acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an ester group, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester protected with a group represented by the formula A).
  • an acetal functional group such as a group
  • a group that is relatively difficult to decompose with an acid for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group.
  • the acid-decomposable group is preferably a group having a structure in which an acid is protected in the form of an acetal from the viewpoints of sensitivity and resolution.
  • the structural unit having an acid group protected with an acid-decomposable group is preferably a structural unit represented by the following formula A from the viewpoint of sensitivity and resolution.
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group or Represents an aryl group, and R 31 or R 32 and R 33 may combine to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or a divalent linking group. Represents.
  • R 31 or R 32 when R 31 or R 32 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R 31 or R 32 is an aryl group, a phenyl group is preferable. R 31 and R 32 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 33 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Further, the alkyl group and aryl group in R 31 to R 33 may have a substituent.
  • R 31 or R 32 and R 33 may be linked to form a cyclic ether, and R 31 or R 32 and R 33 are preferably linked to form a cyclic ether.
  • the number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
  • X 0 represents a single bond or an arylene group, and a single bond is preferable.
  • the arylene group may have a substituent.
  • the structural unit represented by the formula A is a structural unit having a carboxy group protected with an acid-decomposable group. When the polymer contains the structural unit represented by the formula A, the sensitivity at the time of pattern formation is excellent and the resolution is superior.
  • R 34 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the Tg of the polymer can be further lowered. More specifically, the structural unit in which R 34 in Formula A is a hydrogen atom is preferably 20% by mass or more based on the total amount of the structural unit represented by Formula A contained in the polymer.
  • the content (content ratio: mass ratio) of the structural unit in which R 34 in Formula A is a hydrogen atom in the structural unit having an acid group protected with an acid-decomposable group is 13 C-nuclear magnetic resonance. It can be confirmed by the intensity ratio of the peak intensity calculated from the spectrum (NMR) measurement by a conventional method.
  • the structural unit represented by the following formula A2 is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.
  • R 34 represents a hydrogen atom or a methyl group
  • R 35 to R 41 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 34 is preferably a hydrogen atom.
  • R 35 to R 41 are preferably hydrogen atoms.
  • R 34 represents a hydrogen atom or a methyl group.
  • the structural unit having an acid group protected with an acid-decomposable group is preferably a structural unit represented by the following formula A3 from the viewpoint of suppressing deformation of the pattern shape.
  • R B1 and R B2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R B1 and R B2 is an alkyl group or an aryl group, and R B3 is an alkyl group or Represents an aryl group, R B1 or R B2 and R B3 may be linked to form a cyclic ether, R B4 represents a hydrogen atom or a methyl group, and X B represents a single bond or a divalent linking group; R B12 represents a substituent, and n represents an integer of 0 to 4.
  • R B1 or R B2 when R B1 or R B2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R B1 or R B2 is an aryl group, a phenyl group is preferable.
  • R B1 and R B2 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R B3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group and aryl group in R B1 to R B3 may have a substituent.
  • R B1 or R B2 and R B3 may be linked to form a cyclic ether, and R B1 or R B2 and R B3 are preferably linked to form a cyclic ether.
  • the number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
  • X B represents a single bond or a divalent linking group, and represents a single bond or an alkylene group, —C ( ⁇ O) O—, —C ( ⁇ O) NR N —, —O—, or a combination thereof.
  • the alkylene group may be linear, branched or cyclic, and may have a substituent.
  • the alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • X B contains —C ( ⁇ O) O—
  • an embodiment in which the carbon atom contained in —C ( ⁇ O) O— and the carbon atom bonded to R B4 are directly bonded is preferable.
  • R N represents an alkyl group or a hydrogen atom, preferably an alkyl group or a hydrogen atom having 1 to 4 carbon atoms, more preferably a hydrogen atom.
  • R B12 represents a substituent, and is preferably an alkyl group or a halogen atom.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
  • R B4 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of lowering the Tg of the polymer. More specifically, with respect to the total content of the structural unit having an acid group protected by the acid-decomposable group contained in the polymer, the structural unit in which R B4 in formula A3 is a hydrogen atom is 20% by mass or more. It is preferable that In the structural unit having an acid group protected with an acid-decomposable group, the content (content ratio: mass ratio) of the structural unit in which R B4 in formula A3 is a hydrogen atom is 13 C-nuclear magnetic resonance. It can be confirmed by the intensity ratio of the peak intensity calculated from the spectrum (NMR) measurement by a conventional method.
  • the structural unit represented by the following formula A4 is more preferable from the viewpoint of suppressing deformation of the pattern shape.
  • R B4 represents a hydrogen atom or a methyl group
  • R B5 to R B11 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R B12 represents a substituent
  • n is 0 Represents an integer of ⁇ 4.
  • R B4 is preferably a hydrogen atom.
  • R B5 to R B11 are preferably hydrogen atoms.
  • R B12 represents a substituent, and is preferably an alkyl group or a halogen atom.
  • the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
  • R B4 represents a hydrogen atom or a methyl group.
  • the structural unit having an acid group protected by the acid-decomposable group contained in the polymer may be one type or two or more types.
  • the content of the structural unit having an acid group protected by the acid-decomposable group in the polymer is preferably 10% by mass or more with respect to the total mass of the polymer, and is 10% by mass to 90% by mass. More preferred is 20% by mass to 70% by mass.
  • the content (content ratio: mass ratio) of the structural unit having an acid group protected by the acid-decomposable group in the polymer is confirmed by the intensity ratio of the peak intensity calculated by 13 C-NMR measurement by a conventional method. be able to.
  • the content ratio of the structural unit having an acid group protected by the acid-decomposable group in the polymer component is the total content of the polymer components.
  • the mass is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 80% by mass, and particularly preferably 20% by mass to 70% by mass.
  • the mass ratio of the content mass ratio M B of structural units containing a mass ratio M A and pKaH constituent units having protected acid groups in the acid-decomposable group in the polymer component having three or more groups is preferably from 5 to 200, more preferably from 10 to 150, and even more preferably from 20 to 100, from the viewpoints of resolution and retention time-dependent suppression.
  • the polymer in the polymer component is a structural unit other than a structural unit having an acid group protected with an acid-decomposable group and a structural unit having a pKaH of 3 or more (for example, It is preferable to further include a structural unit having an acid group described below and other structural units).
  • the polymers in the polymer component may each independently contain a structural unit having an acid group from the viewpoints of developability and resolution.
  • the structural unit having an acid group is a structural unit having a protective group, for example, an acid group not protected by an acid-decomposable group, that is, an acid group having no protective group.
  • the acid group is usually incorporated into the polymer as a structural unit having an acid group using a monomer capable of forming an acid group.
  • the pKa of the acid group is preferably 10 or less, and more preferably 6 or less.
  • the pKa of the acid group is preferably ⁇ 5 or more.
  • the positive type photosensitive resin layer to be contained has better resolution and sensitivity at the time of pattern formation while maintaining transferability and peelability from the temporary support at good levels.
  • the acid group examples include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonylimide group.
  • at least one acid group selected from the group consisting of a carboxy group and a phenolic hydroxyl group is preferable.
  • Introduction of a structural unit having an acid group into the polymer can be carried out by copolymerizing a monomer having an acid group.
  • the structural unit having an acid group is more preferably a structural unit derived from styrene or a structural unit derived from a vinyl compound, or a structural unit derived from (meth) acrylic acid. preferable.
  • a structural unit having an acid group a structural unit having a carboxy group or a structural unit having a phenolic hydroxyl group is preferable from the viewpoint that sensitivity at the time of pattern formation becomes better.
  • the monomer having an acid group that can form a structural unit having an acid group is not limited to the examples described above.
  • the structural unit having an acid group contained in the polymer may be only one type or two or more types.
  • the polymer having a structural unit having an acid group has a structural unit having an acid group in an amount of 0.1% by mass to 20% by mass with respect to the total mass of the polymer. %, Preferably 0.5% to 15% by weight, more preferably 1% to 10% by weight. When it is in the above range, the pattern formability becomes better.
  • the content (content ratio: mass ratio) of the structural unit having an acid group in the polymer can be confirmed by the intensity ratio of peak intensity calculated by 13 C-NMR measurement by a conventional method.
  • the content rate of the structural unit which has the said acid group in the said polymer component is 0.1 with respect to the total mass of a polymer component.
  • the mass is preferably 20% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and particularly preferably 1% by mass to 10% by mass.
  • the polymer includes other structural units other than the structural unit having an acid group protected with an acid-decomposable group, the structural unit having a pKaH of 3 or more, and the structural unit having an acid group.
  • the photosensitive transfer material according to the present disclosure may be included within a range that does not impair the effect.
  • styrenes (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid Diester, bicyclounsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride, group having aliphatic cyclic skeleton, other Mention may be made of unsaturated compounds.
  • Various characteristics of the polymer can be adjusted by adjusting at least one of the type and content using other structural units.
  • the Tg of the polymer component can be easily adjusted to 90 ° C. or lower by appropriately using other structural units.
  • the polymer may contain only 1 type of other structural units, and may contain 2 or more types.
  • structural units having an aromatic ring or structural units having an aliphatic cyclic skeleton are preferable from the viewpoint of improving the electrical properties of the obtained transfer material.
  • monomers that form these structural units include styrene, tert-butoxystyrene, methylstyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, And benzyl (meth) acrylate etc. are mentioned.
  • the structural unit derived from a cyclohexyl (meth) acrylate is mentioned preferably.
  • (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion.
  • (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion.
  • Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • the content of other structural units is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less with respect to the total mass of the polymer.
  • the lower limit may be 0% by mass, but is preferably 1% by mass or more, and more preferably 5% by mass or more. Within the above range, the resolution and adhesion are further improved.
  • the polymer contained in the said polymer component contains the structural unit which has a carboxylic ester structure from a laminated suitability and a resolution viewpoint each independently.
  • the structural unit having a carboxylic acid ester structure from the viewpoints of laminate suitability and resolution, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate
  • the structural unit derived from is more preferable.
  • the polymer shown in the above a1 or a2 is derived from methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate or benzyl (meth) acrylate from the viewpoint of laminating suitability and resolution. It is preferable to have 2 or more types of structural units derived from methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate or benzyl (meth) acrylate.
  • each of the polymers contained in the polymer component independently contains a structural unit represented by the following formula C as a structural unit having the carboxylic acid ester structure from the viewpoint of laminating suitability and resolution. preferable.
  • R C1 represents a hydrogen atom or a methyl group
  • R C2 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
  • R C2 in Formula C is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 16 carbon atoms from the viewpoint of laminating suitability and resolution. And more preferably a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a benzyl group, and particularly preferably a methyl group, an ethyl group, a cyclohexyl group, or a benzyl group.
  • the polymer shown in a1 or a2 preferably contains 30% by mass or more of a structural unit having a carboxylic acid ester structure with respect to the total mass of the polymer, from the viewpoint of laminating suitability and resolution. More preferably, the content is more preferably 50% by mass to 80% by mass, and particularly preferably 60% by mass to 75% by mass. Moreover, after decomposing
  • the polymer production method is not particularly limited.
  • a polymerizable monomer for forming a structural unit having an acid group protected by an acid-decomposable group, pKaH is 3 or more.
  • the photosensitive resin layer in the present disclosure may contain the polymer component in a proportion of 50% by mass to 99.9% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of developing good adhesion. Preferably, it is contained in a proportion of 70% by mass to 98% by mass.
  • the photosensitive resin layer has, as a polymer component, 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 in addition to the polymer shown in a1 or a2. It may further contain a polymer having no structural unit and a structural unit having pKaH having a group of 3 or more (sometimes referred to as "other polymer").
  • the photosensitive resin layer contains another polymer, the blending amount of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less in the total polymer component, More preferably, it is 20 mass% or less.
  • the said photosensitive resin layer may contain only 1 type of other polymers, and may contain 2 or more types.
  • polymers for example, polyhydroxystyrene can be used and are commercially available, such as SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer).
  • ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 above, manufactured by Toagosei Co., Ltd.
  • Joncryl 690, Joncryl 6 Joncryl 67, Joncryl 586 manufactured by BASF or the like can also be used.
  • the photosensitive resin layer contains a photoacid generator.
  • the photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiation with actinic rays such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
  • the photoacid generator used in the present disclosure is preferably a compound that generates an acid in response to an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but its chemical structure is not limited.
  • a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can be used as a sensitizer as long as it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
  • the photoacid generator used in the present disclosure is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a pKa of 2 or less.
  • a photoacid generator that generates an acid is particularly preferable.
  • the lower limit value of pKa is not particularly defined, but is preferably ⁇ 10.0 or more, for example.
  • the photoacid generator examples include an ionic photoacid generator and a nonionic photoacid generator.
  • the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound described later from the viewpoint of sensitivity and resolution, and an oxime sulfonate compound. It is more preferable to contain.
  • nonionic photoacid generators examples include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
  • the photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion.
  • These photoacid generators can be used singly or in combination of two or more.
  • Specific examples of trichloromethyl-s-triazines and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP 2011-212494A.
  • oxime sulfonate compound that is, a compound having an oxime sulfonate structure
  • a compound having an oxime sulfonate structure represented by the following formula (B1) is preferable.
  • R 21 represents an alkyl group or an aryl group
  • * represents a bonding site with another atom or another group.
  • any group may be substituted, and the alkyl group in R 21 may be linear or branched. It may have a ring structure. Acceptable substituents are described below.
  • the alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • the alkyl group of R 21 is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or other bridged alicyclic group) , Preferably a bicycloalkyl group or the like), or a halogen atom.
  • the aryl group for R 21 is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a naphthyl group.
  • the aryl group of R 21 may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a halogen atom.
  • the compound having an oxime sulfonate structure represented by the formula (B1) is preferably an oxime sulfonate compound described in paragraphs 0078 to 0111 of JP-A-2014-85643.
  • Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, quaternary ammonium salts, and the like. Of these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.
  • ionic photoacid generators described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.
  • a photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
  • the content of the photoacid generator in the photosensitive resin layer is preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of sensitivity and resolution. More preferably, the content is 5% by mass to 5% by mass.
  • the photosensitive resin layer may further contain a basic compound.
  • the molecular weight of the basic compound in the present disclosure is less than 2,000, and preferably less than 1,000.
  • any basic compound used in a chemically amplified positive resist can be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include compounds described in JP-A-2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
  • aliphatic amine examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like.
  • examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
  • aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.
  • heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, and 1,8-diazabicyclo [5.3.0] -7-Undecene.
  • Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
  • Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
  • the said basic compound may be used individually by 1 type, or may use 2 or more types together.
  • the photosensitive resin layer does not contain a basic compound, or the content of the basic compound is preferably more than 0% by mass and 2% by mass or less based on the total mass of the photosensitive resin layer. Whether the basic compound is not included, or the content of the basic compound is preferably more than 0% by mass and 2% by mass or less with respect to the total mass of the photosensitive resin layer, and does not include the basic compound More preferably, the content of the basic compound is more than 0% by mass and 1.2% by mass or less, and particularly preferably no basic compound, with respect to the total mass of the photosensitive resin layer.
  • the said photosensitive resin layer in this indication can contain a well-known additive as needed besides the said component.
  • the photosensitive resin layer preferably contains a surfactant from the viewpoint of film thickness uniformity.
  • a surfactant any of anionic, cationic, nonionic (nonionic), or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. .
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • F-Top manufactured by JEMCO
  • MegaFuck manufactured by DIC Corporation
  • Florard Florard
  • Asahi Guard Surflon (manufactured by Asahi Glass Co., Ltd.)
  • PolyFox manufactured by OMNOVA
  • SH-8400 manufactured by Toray Dow Corning Co., Ltd.
  • a surfactant it contains a structural unit A and a structural unit B represented by the following formula I-1, and is a weight average in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
  • a preferable example is a copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less.
  • R 401 and R 403 each independently represent a hydrogen atom or a methyl group
  • R 402 represents a linear alkylene group having 1 to 4 carbon atoms
  • R 404 represents a hydrogen atom or a carbon group.
  • L represents an alkylene group having 3 to 6 carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p is a numerical value of 10 mass% to 80 mass%.
  • Q represents a numerical value of 20% to 90% by mass
  • r represents an integer of 1 to 18
  • s represents an integer of 1 to 10
  • * represents a bonding site with another structure. Represent.
  • L is preferably a branched alkylene group represented by the following formula (I-2).
  • R 405 in formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred.
  • the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
  • Surfactant may be used individually by 1 type and may use 2 or more types together.
  • the addition amount of the surfactant is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and 0.01% by mass with respect to the total mass of the photosensitive resin layer. More preferably, the content is from 3% to 3% by mass.
  • the photosensitive resin layer may contain at least one polymerization inhibitor.
  • the polymerization inhibitor for example, the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784 can be used. Of these, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.
  • the content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, and 0.01% by mass with respect to the total mass of the photosensitive resin layer. % To 1% by mass is more preferable, and 0.01% to 0.8% by mass is even more preferable.
  • the photosensitive resin layer may contain a solvent.
  • the photosensitive resin composition for forming the photosensitive resin layer is a photosensitive resin composition containing a solvent by adjusting the viscosity of the photosensitive resin composition once by adding a solvent in order to easily form the photosensitive resin layer.
  • the photosensitive resin composition can be applied and dried to suitably form the photosensitive resin layer.
  • a known solvent can be used as the solvent used in the present disclosure.
  • Solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers And diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones.
  • Specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP2011-212494A, the contents of which are incorporated herein.
  • the solvent which can be used for this indication may be used individually by 1 type, and it is more preferable to use 2 types together.
  • two or more solvents for example, combined use of propylene glycol monoalkyl ether acetates and dialkyl ethers, combined use of diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetates A combination with the above is preferred.
  • the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof. Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C.
  • propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), and An example is propylene glycol methyl-n-propyl ether (boiling point 131 ° C.).
  • Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate.
  • the content of the solvent in applying the photosensitive resin composition is preferably 50 parts by weight to 1,900 parts by weight, preferably 100 parts by weight to 100 parts by weight of the total solid content in the photosensitive resin composition. More preferably, it is 900 parts by mass.
  • the content of the solvent in the photosensitive resin layer is preferably 2% by mass or less, more preferably 1% by mass or less, and more preferably 0.5% by mass with respect to the total mass of the photosensitive resin layer. % Or less is more preferable.
  • the photosensitive resin layer may contain a plasticizer for the purpose of improving plasticity.
  • the plasticizer preferably has a weight average molecular weight smaller than that of the polymer represented by a1 or a2.
  • the weight average molecular weight of the plasticizer is preferably from 500 to less than 10,000, more preferably from 700 to less than 5,000, and still more preferably from 800 to 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 and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule.
  • the alkyleneoxy group contained in the plasticizer preferably has the following structure.
  • R represents an alkyl group having 2 to 8 carbon atoms
  • n represents an integer of 1 to 50
  • * represents a bonding site with another atom.
  • compound X a compound having an alkyleneoxy group having the above structure
  • compound X a compound having an alkyleneoxy group having the above structure
  • the resin composition does not fall under the plasticizer in the present disclosure.
  • the optionally added surfactant is generally not used in an amount that brings plasticity to the photosensitive resin composition, and thus does not correspond to the plasticizer in the present specification.
  • plasticizer examples include, but are not limited to, compounds having the following structure.
  • the content of the plasticizer is preferably 1% by mass to 50% by mass and more preferably 2% by mass to 20% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of adhesion. preferable.
  • the said photosensitive resin layer may contain only 1 type of plasticizers, and may contain 2 or more types.
  • the photosensitive resin layer can further contain a sensitizer.
  • the sensitizer absorbs actinic rays and enters an electronically excited state.
  • the sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise
  • anthracene derivative a compound selected from the group consisting of an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a base styryl derivative, and a distyrylbenzene derivative is preferable, and an anthracene derivative is more preferable.
  • Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 1,10-dibromoanthracene, 2-ethylanthracene, or 9,10-dimethoxyanthracene is preferred.
  • Examples of the sensitizer include compounds described in paragraphs 0139 to 0141 of International Publication No. 2015/092731.
  • the content of the sensitizer is preferably 0% by mass to 10% by mass and more preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer.
  • the photosensitive resin layer in the present disclosure can include a heterocyclic compound.
  • a heterocyclic compound There is no restriction
  • Heterocyclic monomers having the following d electrons can be added.
  • the addition amount of the heterocyclic compound in the photosensitive resin layer is preferably 0.01% by mass to 50% by mass with respect to the total mass of the photosensitive resin layer when the heterocyclic compound is added.
  • the content is more preferably 0.1% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass. It is preferable in the said range from a viewpoint of adhesiveness and etching tolerance. Only 1 type may be used for a heterocyclic compound and it can also use 2 or more types together.
  • Specific examples of the compound having an epoxy group in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like.
  • a compound having an epoxy group in the molecule can be obtained as a commercial product.
  • JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Co., Ltd.), JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like commercially available products described in paragraph 0189 of JP2011-221494A, and the like can be mentioned.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and aliphatic epoxy resin is particularly preferable.
  • the compound containing an oxetanyl group is preferably used alone or mixed with a compound containing an epoxy group.
  • the heterocyclic compound is preferably a compound having an epoxy group from the viewpoint of etching resistance and line width stability.
  • the photosensitive resin layer may contain an alkoxysilane compound.
  • Preferred examples of the alkoxysilane compound include trialkoxysilane compounds.
  • Examples of the alkoxysilane compound include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltriacoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, and ⁇ -methacryloxy.
  • ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, ⁇ -glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used alone or in combination of two or more.
  • the photosensitive resin layer in the present disclosure includes metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, and ultraviolet absorption.
  • Known additives such as an agent, a thickener, a crosslinking agent, and an organic or inorganic suspending agent can be further added.
  • Preferred embodiments of the other components are described in JP-A-2014-85643, paragraphs 0165 to 0184, respectively, and the contents of this publication are incorporated herein.
  • the average film thickness of the photosensitive resin layer is preferably 1.0 ⁇ m or more, and more preferably 2.0 ⁇ m or more, from the viewpoint of transferability (laminate).
  • the average film thickness of the photosensitive resin layer is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, from the viewpoint of production suitability.
  • a photosensitive resin composition for forming a photosensitive resin layer can be prepared by mixing each component and a solvent in an arbitrary ratio and by an arbitrary method, and dissolving by stirring. For example, it is possible to prepare a composition by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent.
  • the composition prepared as described above can be used after being filtered using a filter having a pore size of 0.2 ⁇ m or the like.
  • the photosensitive transfer material according to the present disclosure having the photosensitive resin layer on the temporary support can be obtained by applying the photosensitive resin composition on the temporary support or an intermediate layer described later and drying the photosensitive resin composition.
  • the coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
  • the photosensitive resin layer can also be applied after forming other layers described later on the intermediate layer.
  • the photosensitive transfer material according to the present disclosure includes the temporary support and the photosensitive resin layer from the viewpoints of resolution, retention time dependency suppression, adhesion between the intermediate layer and the photosensitive resin layer, and pattern formation. It is preferable to have an intermediate layer between them. Moreover, it is preferable that the said intermediate
  • the binder is preferably a water-soluble or alkali-soluble binder, and more preferably a water-soluble or alkali-soluble polymer.
  • water-soluble means that the solubility in water at pH 7.0 is 0.1% by mass or more at 25 ° C.
  • alkali-soluble means pH 8. It means that the solubility in an alkaline aqueous solution of 5 or more is 0.1% by mass or more.
  • water-soluble or alkali-soluble may be either water-soluble or alkali-soluble, or water-soluble and alkali-soluble.
  • binder examples include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, or m- / p-mixed).
  • novolak resin such as mixed formaldehyde resin, pyrogallol acetone resin, polyhydroxystyrene resin, modified cellulose resin, acrylic resin having a hydroxy group (for example, hydroxyalkyl (meth) acrylate homopolymer or copolymer), Starches, glycogens, chitins, agaroses, carrageenans, pullulans, gum arabic, soya gum, polyamide resin, epoxy resin, polyacetal resin, acrylic resin, polystyrene resin, polyester Urethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyethyleneimine, polyallylamine, polyalkylene glycol, and the like.
  • novolak resin such as mixed formaldehyde resin, pyrogallol acetone resin, polyhydroxystyrene resin, modified cellulose resin, acrylic resin having a hydroxy group (for example, hydroxyalkyl (meth) acrylate homopolymer or copolymer
  • the binder is at least one selected from the group consisting of a novolak resin, a modified cellulose resin, and an acrylic resin having a hydroxy group from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation. It is preferably a resin, more preferably at least one resin selected from the group consisting of a modified cellulose resin and an acrylic resin having a hydroxy group, and more preferably a modified cellulose resin.
  • the modified cellulose resin is preferably hydroxyalkylated cellulose from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation.
  • the hydroxyalkylated cellulose include hydroxymethylcellulose, hydroxyethylcellulose, polyhydroxyethylated cellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, glyoxalized hydroxypropylmethylcellulose, hydroxypropylmethylcellulose phthalate and the like.
  • it is preferably at least one resin selected from the group consisting of hydroxypropylcellulose and hydroxypropylmethylcellulose, and is hydroxypropylmethylcellulose.
  • the binder is preferably at least one resin selected from the group consisting of polyvinyl alcohol and polyvinyl formal from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, and is polyvinyl alcohol. Is more preferable.
  • the weight average molecular weight of the binder is preferably 1,000 or more from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer, pattern formation, solubility in the developer after exposure, and transferability. , Preferably from 100,000 to 100,000, more preferably from 10,000 to 50,000.
  • middle layer may contain the binder individually by 1 type, or may contain 2 or more types.
  • the content of the binder in the intermediate layer is based on the adhesiveness between the intermediate layer and the photosensitive resin layer, pattern formation, solubility in the developer after exposure, and transferability, with respect to the total mass of the intermediate layer, It is preferably 10% by mass or more and 100% by mass or less, more preferably 20% by mass or more and 100% by mass or less, still more preferably 40% by mass or more and 100% by mass or less, and 65% by mass or more and 85% by mass. % Or less is particularly preferable.
  • the intermediate layer in the present disclosure may contain a known additive as required in addition to the binder.
  • other additives used for the photosensitive resin layer are preferably exemplified.
  • the intermediate layer preferably contains particles from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer.
  • the above particles are preferably metal oxide particles or organic particles from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, and oxidation of an element selected from the group consisting of Si, Ti and Zr. More preferably, it is a physical particle or an organic particle.
  • the metal of the metal oxide particles in the present disclosure includes semimetals such as B, Si, Ge, As, Sb, and Te.
  • the metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B , Oxide particles containing atoms such as Al, Si, Ge, Sn, Pb, Sb, Bi, Te, etc. are preferred, silica, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide, or Antimony / tin oxide is more preferable, silica, titanium oxide, titanium composite oxide, or zirconium oxide is more preferable, and silica, titanium oxide, or zirconium oxide is particularly preferable.
  • organic resin particles are preferably exemplified.
  • the organic resin particles include homopolymers and copolymers of acrylic acid monomers such as acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, and cellulose polymers such as nitrocellulose, methylcellulose, ethylcellulose, and cellulose acetate.
  • a condensation polymer such as butadiene-styrene copolymer, a rubber-based thermoplastic polymer such as a butadiene-styrene copolymer, a polymer obtained by polymerizing and crosslinking a photopolymerizable or thermopolymerizable compound such as an epoxy compound, Min compounds and the like.
  • acrylic resin particles are preferable as the organic particles, and polymethyl methacrylate particles are more preferable.
  • the surface of these particles can be treated with an organic material or an inorganic material in order to impart dispersion stability.
  • the particles are preferably particles having a hydrophilic surface.
  • the surface of particles having a hydrophobic surface may be subjected to a hydrophilic treatment.
  • the arithmetic average particle diameter of the particles is preferably 400 nm or less, more preferably 250 nm or less, and further preferably 150 nm or less, from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer.
  • a thickness of 10 nm to 200 nm is particularly preferable.
  • the method for measuring the arithmetic average particle diameter of the particles in the present disclosure refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the maximum diameter is the diameter.
  • the volume fraction of the particles in the intermediate layer (volume ratio of particles in the intermediate layer) is 5% to 90% with respect to the total volume of the intermediate layer from the viewpoint of adhesion between the intermediate layer and the photosensitive layer. It is preferably 10% to 80%, more preferably 15% to 70%, and particularly preferably 20% to 60%.
  • the average film thickness of the intermediate layer is preferably 0.3 ⁇ m to 10 ⁇ m, more preferably 0.3 ⁇ m to 5 ⁇ m, and more preferably 0.3 ⁇ m from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formability. ⁇ 2 ⁇ m is particularly preferred.
  • the average value is preferably measured and calculated at 10 points or more. Specific examples include surface shape measurement and cross-sectional optical microscope or electron microscope observation. In addition, Bruker's Dektak series can be suitably used for surface shape measurement. Moreover, a scanning electron microscope (SEM) can be used suitably for cross-sectional observation.
  • SEM scanning electron microscope
  • the method for forming the intermediate layer is not particularly limited, but each component and a solvent (preferably an aqueous solvent) are mixed at a predetermined ratio and in an arbitrary method, and stirred to dissolve to form the intermediate layer.
  • An intermediate layer forming composition can be prepared. For example, it is possible to prepare a composition by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent.
  • the composition prepared as described above can be used after being filtered using a filter having a pore diameter of 5 ⁇ m.
  • the aqueous solvent include water and water-soluble solvents such as alcohols.
  • the intermediate layer can be easily formed on the temporary support by applying the intermediate layer-forming composition to the temporary support and drying it.
  • the coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
  • an intermediate layer can be applied after forming other layers (for example, a thermoplastic resin layer or the like) described later on the temporary support.
  • the photosensitive transfer material according to the present disclosure may have a layer other than the temporary support, the intermediate layer, and the photosensitive resin layer (hereinafter sometimes referred to as “other layers”).
  • other layers include a contrast enhancement layer, a cover film, and a thermoplastic resin layer.
  • the photosensitive transfer material according to the present disclosure preferably further includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer or the intermediate layer from the viewpoint of transferability.
  • the photosensitive transfer material according to the present disclosure may have a cover film for the purpose of protecting the photosensitive resin layer.
  • Preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP 2014-85643 A, and preferred embodiments of the other layers are described in paragraphs 0194 to 0196 of JP 2014-85643 A, respectively.
  • a thermoplastic resin layer contains the at least 1 sort (s) of thermoplastic resin chosen from the group which consists of an acrylic resin and a styrene / acryl copolymer from a transferable viewpoint.
  • the photosensitive transfer material according to the present disclosure has other layers such as a thermoplastic resin layer
  • the photosensitive transfer material is manufactured according to the method for manufacturing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138. can do.
  • a solution for thermoplastic resin layer
  • a coating solution prepared by adding a resin and an additive to a solvent that does not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer after applying a coating liquid) and drying to provide a thermoplastic resin layer (intermediate)
  • the layer composition is applied and dried to laminate the intermediate layer.
  • a photosensitive transfer material according to the present disclosure is obtained by further applying a photosensitive resin composition prepared using a solvent that does not dissolve the intermediate layer on the formed intermediate layer, and drying and laminating the photosensitive resin layer. Can be suitably produced.
  • a contrast enhancement layer is a material that absorbs light with respect to an exposure wavelength before exposure, but gradually decreases with exposure, that is, a material that increases light transmittance (photodecoloration). It is a layer containing a coloring pigment component).
  • photodecolorable dye components include diazonium salts, stilbazolium salts, arylnitroso salts, and the like.
  • a phenolic resin or the like is used as the film forming component.
  • the method for producing a resin pattern according to the present disclosure is not particularly limited as long as it is a method for producing a resin pattern using the photosensitive transfer material according to the present disclosure, but the photosensitive resin in the photosensitive transfer material according to the present disclosure.
  • the circuit wiring manufacturing method according to the present disclosure is not particularly limited as long as it is a circuit wiring manufacturing method using the photosensitive transfer material according to the present disclosure.
  • the substrate is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface.
  • photosensitive resin compositions are classified into a negative type in which a portion irradiated with actinic rays is left as an image and a positive type in which a portion not irradiated with actinic rays is left as an image due to differences in photosensitive systems.
  • the positive type by irradiating actinic rays, for example, to improve the solubility of the exposed portion using a photosensitive agent that generates acid upon irradiation with actinic rays, both the exposed and unexposed portions are exposed at the time of pattern exposure. If the pattern shape obtained is not cured and the substrate is defective, the substrate can be reused (reworked) by full exposure or the like.
  • the positive type is preferable from the viewpoint of excellent so-called reworkability.
  • the technique of reexposing the remaining photosensitive resin layer to produce a different pattern can be realized only by the photosensitive resin layer, the resin pattern manufacturing method according to the present disclosure or the circuit according to the present disclosure In the method for producing a wiring, an embodiment in which exposure is performed twice or more is preferable.
  • a method for manufacturing a resin pattern according to the present disclosure or a method for manufacturing a circuit wiring according to the present disclosure is provided by contacting the photosensitive resin layer in the photosensitive transfer material according to the present disclosure with a substrate, preferably a substrate having a conductive layer. It is preferable to include the process of bonding together (bonding process). Moreover, in the said bonding process, it is preferable to make it pressure-bond so that the said conductive layer and the said photosensitive resin layer may contact.
  • the patterned photosensitive resin layer after exposure and development can be suitably used as an etching resist when the conductive layer is etched.
  • the photosensitive resin layer side of the photosensitive transfer material is preferably overlapped on a substrate and pressed by a roll or the like, or pressed and heated.
  • laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
  • the pressure and temperature of the bonding in the bonding step there are no particular limitations on the pressure and temperature of the bonding in the bonding step, and it depends on the surface material of the substrates to be bonded, for example, the material of the conductive layer, the material of the photosensitive resin layer, the conveyance speed, and the pressure bonding machine used. Can be set as appropriate. Moreover, what is necessary is just to crimp
  • the substrate used in the present disclosure is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface of a base material.
  • a wiring is formed by patterning the conductive layer.
  • several electroconductive layers such as a metal oxide and a metal, were provided in film base materials, such as a polyethylene terephthalate.
  • substrate used for this indication is a board
  • the said conductive layer is a layer containing copper from a viewpoint which exhibits the effect in this indication more.
  • the substrate is preferably a substrate in which a plurality of conductive layers are stacked on a support.
  • a support body is a glass base material or a film base material, and it is more preferable that it is a film base material.
  • the support is particularly preferably a sheet-shaped resin composition.
  • the support is preferably transparent.
  • the refractive index of the support is preferably 1.50 to 1.52.
  • the support may be composed of a translucent substrate such as a glass substrate, and tempered glass represented by Corning's gorilla glass can be used.
  • materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.
  • a film substrate is used as the substrate, it is more preferable to use a substrate that is not optically distorted and a substrate having high transparency.
  • Specific examples of the material include polyethylene terephthalate (PET), Examples thereof include polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.
  • Examples of the conductive layer include any conductive layer used for general wiring or touch panel wiring.
  • Examples of the material for the conductive layer include metals and metal oxides.
  • Examples of the metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO 2 .
  • Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, and Mo.
  • At least one of the plurality of conductive layers includes a metal oxide.
  • the conductive layer is preferably an electrode pattern corresponding to a sensor for a visual recognition part used in a capacitive touch panel or a wiring for a peripheral extraction part.
  • the manufacturing method of the resin pattern which concerns on this indication, or the manufacturing method of the circuit wiring which concerns on this indication includes the process (exposure process) of carrying out pattern exposure of the said photosensitive resin layer after the said bonding process.
  • the photosensitive resin layer is preferably irradiated with actinic rays through a mask having a predetermined pattern.
  • the photoacid generator is decomposed to generate an acid.
  • the acid-decomposable group contained in the coating film component is hydrolyzed to produce an acid group, for example, a carboxy group or a phenolic hydroxyl group.
  • the detailed arrangement and specific size of the pattern are not particularly limited. Since it is desired to improve the display quality of a display device (for example, a touch panel) including an input device having a circuit board manufactured in the present disclosure and to minimize the area occupied by the extraction wiring, at least a part of the pattern (particularly the touch panel)
  • the electrode pattern and the part of the lead-out wiring) are preferably fine wires of 100 ⁇ m or less, and more preferably 70 ⁇ m or less.
  • the exposure in the exposure step may be exposure through a mask or digital exposure using a laser or the like, but is preferably exposure through an exposure mask.
  • the method for producing a resin pattern according to the present disclosure or the method for producing a circuit wiring according to the present disclosure includes a step of bringing the photosensitive transfer material and an exposure mask into contact between the bonding step and the exposure step. It is preferable to contain. It is excellent in the resolution of the pattern obtained as it is the said aspect.
  • Visible light, ultraviolet light, and an electron beam are mentioned as actinic light, However, Visible light or ultraviolet light is preferable and an ultraviolet-ray is especially preferable.
  • an exposure light source using actinic light a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generator, etc. can be used.
  • Actinic rays having a wavelength of 300 nm to 450 nm, such as h-line (405 nm), can be preferably used.
  • irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
  • Exposure dose depending on the photosensitive resin layer to be used may be appropriately selected, but is preferably from 5mJ / cm 2 ⁇ 200mJ / cm 2, more preferably 10mJ / cm 2 ⁇ 100mJ / cm 2 . It is also preferable to perform heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure.
  • PEB Post Exposure Bake
  • pattern exposure performs after peeling a temporary support body from the photosensitive resin layer, before peeling a temporary support body, it exposes through a temporary support body, and peels a temporary support body after that. Also good.
  • the pattern exposure may be exposure through a mask or digital exposure using a laser or the like.
  • the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure includes a step of developing the exposed photosensitive resin layer to form a pattern after the exposing step (developing step). It is preferable to contain.
  • the photosensitive transfer material has an intermediate layer
  • the exposed intermediate layer is also removed together with the exposed photosensitive resin layer in the development step.
  • the intermediate layer in the unexposed area may also be removed in a form of being dissolved or dispersed in the developer.
  • Development of the exposed photosensitive resin layer in the development step can be performed using a developer.
  • the developer is not particularly limited as long as the exposed portion of the photosensitive resin layer can be removed.
  • a known developer such as the developer described in JP-A No.
  • the developer is preferably a developer in which the exposed portion of the photosensitive resin layer exhibits a dissolution type development behavior.
  • the developer is preferably an alkaline aqueous solution, and more preferably, for example, an alkaline aqueous solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L.
  • the developer may further contain an organic solvent miscible with water, a surfactant, and the like. Examples of the developer suitably used in the present disclosure include the developer described in Paragraph 0194 of International Publication No. 2015/092731.
  • the development method is not particularly limited, and any of paddle development, shower development, shower and spin development, dip development, and the like may be used.
  • the shower development will be described.
  • the exposed portion can be removed by spraying the developer onto the exposed photosensitive resin layer by shower. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
  • the liquid temperature of the developer is preferably 20 ° C. to 40 ° C. Moreover, the effect which suppresses the deformation
  • a method for manufacturing a resin pattern according to the present disclosure or a method for manufacturing a circuit wiring according to the present disclosure includes a step of washing with water after development, a step of drying a substrate having the obtained pattern, and the like. These steps may be included.
  • the post-baking process which heat-processes the pattern obtained by image development.
  • the post-baking is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably in an environment of 50.66 kPa or more. On the other hand, it is more preferable to carry out in an environment of 111.46 kPa or less, and it is particularly preferable to carry out in an environment of 101.3 kPa or less.
  • the post-baking temperature is preferably 80 ° C. to 250 ° C., more preferably 110 ° C. to 170 ° C., and particularly preferably 130 ° C. to 150 ° C.
  • the post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
  • the post-bake may be performed in an air environment or a nitrogen substitution environment.
  • the transport speed of the support in each step of the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure is not particularly limited. It is preferably from min to 10 m / min, and more preferably from 2.0 m / min to 8.0 m / min except during exposure.
  • the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure peels off the temporary support after the step of bonding to the substrate and before the step of forming the pattern. It is preferable to include a process (peeling process).
  • the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure uses the photosensitive transfer material. Therefore, after the photosensitive transfer material is bonded to each other and at any timing before development, Even if the support is peeled off, the adhesiveness with the photosensitive resin layer is excellent, so that the cause of defects such as partial peeling is suppressed, and the pattern can be formed satisfactorily.
  • the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure includes a step of bonding the substrate to the substrate and the photosensitive resin layer from the viewpoint of pattern formability and resolution. It is more preferable that a step of peeling the temporary support is included before the pattern exposure step. Further, in the case of the above-described aspect, when pattern exposure is performed with a mask in contact, the photosensitive resin layer and the mask are not in direct contact with each other, so that the pattern formability and resolution are excellent. There is no restriction
  • the circuit wiring manufacturing method preferably includes a step (etching step) of etching the conductive layer in a region where the pattern is not disposed.
  • the conductive layer is etched using the pattern formed from the photosensitive resin layer in the developing step as an etching resist.
  • Etching of the conductive layer can be performed by a known method such as a method described in paragraphs 0048 to 0054 of JP 2010-152155 A or a dry etching method such as a known plasma etching.
  • a known method such as a method described in paragraphs 0048 to 0054 of JP 2010-152155 A
  • a dry etching method such as a known plasma etching.
  • a commonly performed wet etching method in which the substrate is immersed in an etching solution can be used.
  • an acid type or alkaline type etchant may be appropriately selected in accordance with an object to be etched.
  • Acidic etchants include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, aqueous solutions of acidic components such as phosphoric acid, acidic components and ferric chloride, ammonium fluoride, or permanganese Examples thereof include a mixed aqueous solution of a salt such as potassium acid.
  • the acidic component a component obtained by combining a plurality of acidic components may be used.
  • Alkali type etching solutions include sodium hydroxide, potassium hydroxide, ammonia, organic amines, or aqueous solutions of alkali components such as organic amine salts such as tetramethylammonium hydroxide, alkaline components and potassium permanganate.
  • alkali components such as organic amine salts such as tetramethylammonium hydroxide, alkaline components and potassium permanganate.
  • a mixed aqueous solution of a salt such as As the alkali component, a component obtained by combining a plurality of alkali components may be used.
  • the temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower.
  • the pattern used as an etching mask preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower. Therefore, the pattern is prevented from peeling off during the etching process, and a portion where the pattern does not exist is selectively etched.
  • a process of cleaning the etched substrate (cleaning process) and a process of drying the etched substrate (drying process) are performed as necessary. Also good.
  • the cleaning step for example, the substrate may be cleaned with pure water for 10 seconds to 300 seconds at room temperature (10 ° C. to 35 ° C.).
  • the drying step for example, air blow may be used, and the air blow pressure (about 0.1 kg / cm 2 to about 5 kg / cm 2 ) may be appropriately adjusted for drying.
  • the manufacturing method of the circuit wiring which concerns on this indication includes the process (etching resist peeling process) which peels the said photosensitive resin layer using peeling liquid after the said etching process. After the etching process is finished, the patterned photosensitive resin layer remains. If the photosensitive resin layer is unnecessary, all the remaining photosensitive resin layers may be removed.
  • a method of peeling using a peeling solution for example, a substrate having the above-mentioned photosensitive resin layer or the like in the peeling solution preferably stirred at 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 5 minutes. Examples include a method of immersing for ⁇ 30 minutes.
  • an inorganic alkali component such as sodium hydroxide or potassium hydroxide, or an organic alkali component such as a tertiary amine or quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or And a stripping solution dissolved in a mixed solution thereof.
  • a stripping solution may be used and stripped by a spray method, a shower method, a paddle method, or the like.
  • the manufacturing method of the circuit wiring which concerns on this indication may repeat an exposure process, a image development process, and an etching process twice or more as needed.
  • the exposure step, the development step, and other steps in the present disclosure the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present disclosure.
  • the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure may include other optional steps.
  • the following processes are mentioned, it is not limited to these processes.
  • the manufacturing method of the circuit wiring according to the present disclosure may include a process of reducing the visible light reflectivity of the surface of the conductive layer, for example, a part or all of the surface of the conductive layer on the substrate.
  • the treatment for reducing the visible light reflectance include an oxidation treatment.
  • the visible light reflectance can be reduced by blackening the copper by oxidizing copper.
  • paragraphs 0017 to 0025 of JP2014-150118A, and paragraphs 0041, 0042, 0048 and 0058 of JP2013-206315A are described. The contents of this publication are incorporated herein.
  • a method of manufacturing a circuit wiring according to the present disclosure includes a step of forming an insulating film on the substrate, for example, a formed wiring (etched conductive layer), and a step of forming a new conductive layer on the insulating film. It is also preferable to contain.
  • an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.
  • a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
  • the new conductive layer may be etched by forming an etching resist by a method similar to the above, or may be separately etched by a known method.
  • the substrate having the circuit wiring obtained by the circuit wiring manufacturing method according to the present disclosure may have only one layer of wiring on the substrate, or may have two or more layers of wiring.
  • the substrate may have a plurality of conductive layers on both surfaces, and the circuit may be sequentially or simultaneously formed on the conductive layers formed on both surfaces of the substrate.
  • a wiring in which a first conductive pattern (first wiring) is formed on one surface of the substrate and a second conductive pattern (second wiring) is formed on the other surface, preferably a touch panel wiring. can be formed.
  • the circuit wiring according to the present disclosure is a circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure.
  • substrate which has the circuit wiring which concerns on this indication is a board
  • substrate which has the circuit wiring which concerns on this indication is not limited, For example, it is preferable that it is a circuit wiring board for touchscreens.
  • the input device is mentioned as an apparatus provided with the circuit wiring manufactured by the manufacturing method of the circuit wiring concerning this indication.
  • the input device according to the present disclosure may be an input device having at least a circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure, and is preferably a capacitive touch panel.
  • the display device according to the present disclosure preferably includes the input device according to the present disclosure.
  • the display device according to the present disclosure is preferably an organic EL display device and an image display device such as a liquid crystal display device.
  • the touch panel according to the present disclosure is a touch panel having at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure.
  • the touch panel according to the present disclosure preferably includes at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
  • the touch panel display device according to the present disclosure is a touch panel display device having at least circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure, and is preferably a touch panel display device including the touch panel according to the present disclosure.
  • the touch panel manufacturing method according to the present disclosure is not particularly limited as long as it is a touch panel manufacturing method using the photosensitive transfer material according to the present disclosure, but the photosensitive resin of the photosensitive transfer material according to the present disclosure.
  • a step of bringing a layer into contact with a substrate having a conductive layer, a step of pattern-exposing the photosensitive resin layer, a step of developing the exposed photosensitive resin layer to form a pattern, and the pattern It is preferable to include a step of etching the conductive layer in a region where no is disposed.
  • any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Among these, the electrostatic capacity method is preferable.
  • a so-called in-cell type for example, those described in FIGS. 5, 6, 7, and 8 of JP-T-2012-517051
  • a so-called on-cell type for example, JP 2013-168125 A
  • OGS One Glass Solution
  • TOL Touch-on-Lens
  • other configurations for example, those shown in FIG. 6 of JP2013-164671A
  • various out-cell types for example, GG, G1, G2, GFF, GF2, GF1, G1F, etc.
  • ATHF 2-tetrahydrofuranyl acrylate (synthetic product)
  • MATHF 2-tetrahydrofuranyl methacrylate (synthetic product)
  • TBA tert-butyl acrylate (Fuji Film Wako Pure Chemical Industries, Ltd.)
  • AA Acrylic acid (Fuji Film Wako Pure Chemical Industries, Ltd.)
  • EA ethyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
  • MMA Methyl methacrylate (Fuji Film Wako Pure Chemical Industries, Ltd.)
  • CHA cyclohexyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
  • BMA benzyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
  • ⁇ Photo acid generator> B-1 Compound having the structure shown below (Compound described in paragraph 0227 of JP 2013-47765 A, synthesized according to the method described in paragraph 0227)
  • Ts represents a tosyl group.
  • B-4 GSID-26-1, triarylsulfonium salt (manufactured by BASF, the following compound)
  • D-2 2-Phenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • D-3 Trioctylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • the coating was applied so that the dry film thickness was 3.0 ⁇ m and the coating width was 1.0 m. Thereafter, the film is passed through a drying zone at 80 ° C. for 40 seconds, a polyethylene film (OSM-N, manufactured by Tredegar) is pressure-bonded as a cover film to produce a photosensitive transfer material, and the photosensitive transfer material is taken up and rolled. Formed.
  • OSM-N polyethylene film
  • a PET substrate with a copper layer in which copper was deposited to a thickness of 200 nm on a PET film having a thickness of 100 ⁇ m by a vacuum deposition method was used.
  • the produced photosensitive transfer material was cut into a 50 cm square, the cover film was peeled off, and the roll temperature was 90 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 4.0 m / min. It laminated on the said PET board
  • Area ratio (%) area where the intermediate layer and the photosensitive resin layer adhere / area of the entire sample piece ⁇ 100 5: 95% or more 4: 90% or more and less than 95% 3: 85% or more and less than 90% 2: 80% or more and less than 85% 1: less than 80%
  • the exposure amount is preferably less than 200 mJ / cm 2 . 5: 80mJ / cm 2 less than 4: 80mJ / cm 2 or more 150 mJ / cm 2 less than 3: 150mJ / cm 2 or more 200 mJ / cm 2 less than 2: 200mJ / cm 2 or more 300 mJ / cm 2 less than 1: 300mJ / cm 2 or more
  • the roll temperature was 120 ° C.
  • the linear pressure was 1.0 MPa
  • the linear velocity was 0.5 m / min.
  • Lamination was performed on a PET substrate with a copper layer under the laminating conditions. Without exposing the temporary support, it was left at 25 ° C. for 12 hours after exposure with the exposure amount with no residue in the sensitivity evaluation through a line and space pattern mask (Duty ratio 1: 1) having a line width of 10 ⁇ m. Thereafter, the temporary support was peeled off and developed. Development was performed by shower development for 30 seconds using a 1.0% aqueous sodium carbonate solution at 25 ° C.
  • the line width of the obtained line and space pattern was observed with a scanning electron microscope (SEM), and the fluctuation of the line width from 10 ⁇ m was evaluated.
  • the line width variation from 10 ⁇ m is preferably less than 1.5 ⁇ m. 5: Less than 0.5 ⁇ m 4: 0.5 ⁇ m or more and less than 1.0 ⁇ m 3: 1.0 ⁇ m or more and less than 1.5 ⁇ m 2: 1.5 ⁇ m or more and less than 3 ⁇ m 1: 3 ⁇ m or more
  • the produced photosensitive transfer material was subjected to a roll temperature of 120 ° C., a linear pressure of 0.8 MPa, and a linear velocity of 1.0 m / min. It laminated on the PET board
  • the copper layer was etched by a dipping method for 60 seconds using a copper etching solution at 25 ° C. (Cu-02 manufactured by Kanto Chemical Co., Inc.).
  • the remaining photosensitive resin layer was peeled off with a shower using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.) at 50 ° C. to form a copper wiring having a conductive pattern with a line and space of 10 ⁇ m.
  • the copper wiring LWR Line Width Roughness, 3 ⁇ of a value obtained by measuring the width of the copper wiring at 250 points
  • LWR Line Width Roughness, 3 ⁇ of a value obtained by measuring the width of the copper wiring at 250 points
  • LWR is 230 nm or less and more than 200 nm.
  • Table 2 summarizes the evaluation results in each example and each comparative example.
  • the photosensitive transfer materials of Examples 1 to 17 are superior in laminate suitability and resolution as compared with the photosensitive transfer materials of Comparative Examples 1 to 5. Further, from the above Table 2, the photosensitive transfer materials of Examples 1 to 17 are excellent in sensitivity and retention time dependence suppression.
  • Example 101 On the 100 ⁇ m-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer at a thickness of 200 nm by vacuum evaporation. Thus, a circuit forming substrate was obtained.
  • the photosensitive transfer material obtained in Example 1 was laminated on the copper layer (Lamiroll temperature 120 ° C., linear pressure 0.8 MPa, linear velocity 1.0 m / min.).
  • a photomask provided with a pattern hereinafter also referred to as “pattern A”) shown in FIG. 2 having a structure in which conductive layer pads are connected in one direction without peeling off the temporary support from the laminated support is used.
  • the contact pattern was exposed.
  • the solid line portion SL and the gray portion G are light shielding portions, and the dotted line portion DL virtually shows an alignment alignment frame.
  • the temporary support was peeled off, developed and washed with water to obtain a pattern A.
  • the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), A substrate on which both copper and ITO were drawn in pattern A was obtained.
  • pattern alignment was performed using a photomask provided with openings of a pattern shown in FIG.
  • pattern B in the aligned state, and development and washing were performed.
  • the gray portion G is a light shielding portion
  • the dotted line portion DL is a virtual alignment alignment frame.
  • the copper layer was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
  • KP-301 manufactured by Kanto Chemical Co., Inc.
  • Example 102 On the 100 ⁇ m-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer at a thickness of 200 nm by vacuum evaporation. Thus, a circuit forming substrate was obtained.
  • the photosensitive transfer material obtained in Example 1 was unwound and laminated on the copper layer (roll temperature 120 ° C., linear pressure 0.8 MPa, linear velocity 1.0 m / min.).
  • the laminated support was subjected to pattern exposure using a photomask provided with a pattern A having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support.
  • the temporary support was peeled off, developed and washed with water to obtain a pattern A.
  • the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), A substrate on which both copper and ITO were drawn in pattern A was obtained.
  • PET (A) was laminated as a protective layer on the remaining resist. In this state, pattern exposure was performed using a photomask provided with an opening of pattern B in the aligned state, and after developing PET (A), development and washing were performed.
  • the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was stripped using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
  • a stripping solution KP-301 manufactured by Kanto Chemical Co., Inc.
  • Example 103 On the 100 ⁇ m-thick cycloolefin polymer (COP) substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer by a thickness of 200 nm by vacuum evaporation. To form a substrate for forming a conductive pattern.
  • the photosensitive transfer material obtained in Example 1 was bonded to a substrate on a copper layer (roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.) To obtain a laminate.
  • the laminate was subjected to pattern exposure using a photomask provided with a pattern A having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a resin pattern drawn with pattern A.
  • the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), and a peeling solution.
  • KP-301 manufactured by Kanto Chemical Co., Inc.
  • the photosensitive transfer material obtained in Example 1 was bonded onto the remaining resist (roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.).
  • pattern exposure was performed using a photomask provided with openings of pattern B in the aligned state, and the temporary support of the photosensitive transfer material was peeled off, followed by development and washing with water.
  • the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board having a conductive pattern. .
  • KP-301 manufactured by Kanto Chemical Co., Inc.

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Abstract

A photosensitive transfer material comprising a temporary support and a photosensitive resin layer, wherein the photosensitive resin layer contains a polymer component which meets at least one of the requirements a1 and a2 and a photo-acid generator, and the polymer component has a glass transition temperature of 90°C or lower; and a method for producing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel, each using the photosensitive transfer material. a1: A polymer component which comprises a polymer that has both of a constituent unit having an acid group protected by an acid-degradable group and a constituent unit having a group having a pKaH value of 3 or more; and a2: a polymer component which comprises both of a polymer that has a constituent unit having an acid group protected by an acid-degradable group and a polymer that has a constituent unit having a group having a pKaH value of 3 or more.

Description

感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法Photosensitive transfer material, resin pattern manufacturing method, circuit wiring manufacturing method, and touch panel manufacturing method
　本開示は、感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法に関する。 The present disclosure relates to a photosensitive transfer material, a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method.
　静電容量型入力装置などのタッチパネルを備えた表示装置（有機エレクトロルミネッセンス（ＥＬ）表示装置及び液晶表示装置など）では、視認部のセンサーに相当する電極パターン、周辺配線部分及び取り出し配線部分の配線などの導電層パターンがタッチパネル内部に設けられている。
　一般的にパターン化した層の形成には、必要とするパターン形状を得るための工程数が少ないといったことから、感光性転写材料を用いて任意の基板上に設けた感光性樹脂組成物の層に対して、所望のパターンを有するマスクを介して露光した後に現像する方法が広く使用されている。 In a display device (such as an organic electroluminescence (EL) display device and a liquid crystal display device) having a touch panel such as a capacitance type input device, an electrode pattern corresponding to a sensor of a visual recognition part, a wiring of a peripheral wiring part, and a lead-out wiring part A conductive layer pattern such as is provided inside the touch panel.
In general, a patterned layer is formed by a photosensitive resin composition layer provided on an arbitrary substrate using a photosensitive transfer material because the number of steps for obtaining a required pattern shape is small. On the other hand, a method of developing after exposure through a mask having a desired pattern is widely used.
　また、従来の感光性樹脂組成物としては、特許文献１又は２に記載されたものが知られている。
　従来の方法としては、例えば、特許文献１には、（Ａ）下記（１）及び（２）の少なくとも一方を満たす重合体を含む重合体成分、（１）（ａ－１）酸基が酸分解性基で保護された基を有する構成単位、及び（ａ－２）架橋性基を有する構成単位、を有する重合体、（２）（ａ－１）酸基が酸分解性基で保護された基を有する構成単位を有する重合体、及び（ａ－２）架橋性基を有する構成単位を有する重合体、（Ｂ）光酸発生剤、（Ｃ）溶剤、並びに（Ｓ）一般式（１）で表される構成単位、及び一般式（２）で表される構成単位を有する重合体を含有し、上記重合体（Ｓ）は、上記重合体（Ｓ）の全繰り返し単位中における一般式（２）で表される構成単位のモル比率が、上記重合体（Ｓ）の全繰り返し単位中における一般式（１）で表される構成単位のモル比率の０．３～５倍である、感光性樹脂組成物が開示されている。 Moreover, what was described in patent document 1 or 2 is known as a conventional photosensitive resin composition.
As a conventional method, for example, in Patent Document 1, (A) a polymer component containing a polymer satisfying at least one of the following (1) and (2), (1) (a-1) an acid group is an acid A polymer having a structural unit having a group protected by a decomposable group, and (a-2) a structural unit having a crosslinkable group, and (2) (a-1) the acid group is protected by an acid-decomposable group. (A-2) a polymer having a structural unit having a crosslinkable group, (B) a photoacid generator, (C) a solvent, and (S) a general formula (1) ) And a polymer having a structural unit represented by the general formula (2), the polymer (S) is a general formula in all repeating units of the polymer (S). The molar ratio of the structural unit represented by (2) is represented by the general formula (1) in all repeating units of the polymer (S). 0.3 to 5 times the molar ratio of structural units, the photosensitive resin composition is disclosed.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（１）及び（２）中、Ｒ10及びＲ11は、それぞれ独立に、水素原子又は、メチル基を表し、Ｌ1及びＬ2は、それぞれ独立に、単結合、又は、２価の連結基を表し、Ｒ1～Ｒ4は、それぞれ独立に、炭素数１～１２のアルキル基又は炭素数１～１２のアルコキシ基を表し、Ｒ5は、水素原子、炭素数１～１２のアルキル基又は炭素数１～１２のアルコキシ基を表す。 In formulas (1) and (2), R 10 and R 11 each independently represent a hydrogen atom or a methyl group, and L 1 and L 2 each independently represent a single bond or a divalent linkage. R 1 to R 4 each independently represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and R 5 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or Represents an alkoxy group having 1 to 12 carbon atoms.
　また、特許文献２には、少なくとも、下記一般式（１）で示される、酸不安定基で置換されたカルボキシル基を有する繰り返し単位ａ、スルホニウム塩を有する繰り返し単位ｂ１及びｂ２のいずれか１つ以上、アミノ基を有する繰り返し単位ｃを有する高分子化合物を含むことを特徴とするレジスト材料が開示されている。 Patent Document 2 discloses at least one of repeating unit a having a carboxyl group substituted with an acid labile group and repeating units b1 and b2 having a sulfonium salt represented by the following general formula (1). As described above, a resist material comprising a polymer compound having a repeating unit c having an amino group has been disclosed.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
（式中、Ｒ１、Ｒ３、Ｒ８、Ｒ１２はそれぞれ独立に、水素原子、メチル基、フッ素原子、又はトリフルオロメチル基を表す。Ｒ２は酸不安定基を表す。Ｘは単結合、フェニレン基、又はナフチレン基であるか、あるいはエステル基、ラクトン環を有する炭素数１～１２の連結基である。Ｒ４は炭素数１～１０のアルキレン基、又は炭素数６～１０のアリーレン基であり、フッ素原子、トリフルオロメチル基、エステル基、エーテル基、ラクトン環を有していても良い。Ｒ５、Ｒ６、Ｒ７、Ｒ９、Ｒ１０、Ｒ１１は同一、又は異種の炭素数１～１２の直鎖状、分岐状又は環状のアルキル基であり、カルボニル基、エステル基又はエーテル基を含んでいてもよく、又は炭素数６～１２のアリール基、炭素数７～２０のアラルキル基又はチオフェニル基を表し、炭素数１～１０のアルキル基、アルコキシ基、アルコキシカルボニル基、カーボネート基、及びハロゲン原子、シアノ基、ヒドロキシル基、カルボキシル基を置換基として有していても良い。Ｙは単結合、メチレン基、フッ素原子若しくはトリフルオロメチル基で置換されたアリーレン基、又は－Ｃ（＝Ｏ）－Ｏ－Ｒ１７－である。Ｒ１７はフッ素原子又はトリフルオロメチル基で置換されたアリーレン基である。Ｒ１３は単結合、又は炭素数１～１０の直鎖状、分岐状若しくは環状のアルキレン基、Ｒ１４、Ｒ１５はそれぞれ独立に、水素原子、炭素数１～２０直鎖状、分岐状若しくは環状のアルキル基、ｔ－ブトキシカルボニル基、又はｔ－アリロキシカルボニル基で、エーテル結合、チオエーテル結合、ヒドロキシル基、ホルミル基、アセトキシ基、シアノ基、芳香族基を有していてもよく、Ｒ１３とＲ１４、Ｒ１３とＲ１５、Ｒ１４とＲ１５がそれぞれ結合して環を形成していても良い。Ｒ１６は水素原子又はＲ１５と結合して環を形成していても良い。Ｚは単結合、メチレン基、アリーレン基、－Ｏ－、－Ｃ（＝Ｏ）－Ｏ－又は－Ｃ（＝Ｏ）－Ｏ－Ｒ１８－Ｃ（＝Ｏ）－Ｏ－、である。Ｒ１８は単結合、又は炭素数１～１０の直鎖状、分岐状若しくは環状のアルキレン基である。０＜ａ＜１．０、０≦ｂ１≦０．３、０≦ｂ２≦０．３、０＜ｂ１＋ｂ２≦０．３、０＜ｃ≦０．５の範囲である。） (In the formula, R 1 , R 3 , R 8 and R 12 each independently represents a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group. R 2 represents an acid labile group. X represents a single group. A bond, a phenylene group, or a naphthylene group, or an ester group or a linking group having a lactone ring and having 1 to 12 carbon atoms, R 4 is an alkylene group having 1 to 10 carbon atoms, or 6 to 10 carbon atoms An arylene group which may have a fluorine atom, a trifluoromethyl group, an ester group, an ether group or a lactone ring, and R 5 , R 6 , R 7 , R 9 , R 10 and R 11 are the same, or It is a different type of linear, branched or cyclic alkyl group having 1 to 12 carbon atoms and may contain a carbonyl group, an ester group or an ether group, or an aryl group having 6 to 12 carbon atoms, or a carbon number 7 ~ 20 Aralkyl Or a thiophenyl group, which may have an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkoxycarbonyl group, a carbonate group, and a halogen atom, a cyano group, a hydroxyl group, or a carboxyl group as a substituent. A single bond, a methylene group, an arylene group substituted with a fluorine atom or a trifluoromethyl group, or —C (═O) —O—R 17 —, wherein R 17 is substituted with a fluorine atom or a trifluoromethyl group R 13 is a single bond, or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, R 14 and R 15 are each independently a hydrogen atom or a linear chain having 1 to 20 carbon atoms. An alkyl group, branched or cyclic alkyl group, t-butoxycarbonyl group, or t-allyloxycarbonyl group, an ether bond, a thioether bond , Hydroxyl group, formyl group, an acetoxy group, a cyano group, may have an aromatic group, and R 13 and R 14, R 13 and R 15, R 14 and R 15 are respectively bonded to form a ring R 16 may be bonded to a hydrogen atom or R 15 to form a ring, Z is a single bond, a methylene group, an arylene group, —O—, —C (═O) —O—, or —C (═O) —O—R 18 —C (═O) —O—, wherein R 18 is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. 0 <a <1.0, 0 ≦ b1 ≦ 0.3, 0 ≦ b2 ≦ 0.3, 0 <b1 + b2 ≦ 0.3, and 0 <c ≦ 0.5.)
　更に、従来の感光性転写材料としては、特許文献３に記載されたものが知られている。
　特許文献３には、仮支持体と、下記一般式Ａで表される構成単位及び酸基を有する構成単位を含み、かつ、ガラス転移温度が９０℃以下である重合体、並びに光酸発生剤を含むポジ型感光性樹脂層と、を有する感光性転写材料が開示されている。 Further, as a conventional photosensitive transfer material, one described in Patent Document 3 is known.
Patent Document 3 includes a temporary support, a polymer having a structural unit represented by the following general formula A and a structural unit having an acid group, and having a glass transition temperature of 90 ° C. or lower, and a photoacid generator. There is disclosed a photosensitive transfer material having a positive photosensitive resin layer containing.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　一般式Ａ中、Ｒ３１及びＲ３２はそれぞれ独立に、水素原子、アルキル基又はアリール基を表し、少なくともＲ３１及びＲ３２のいずれか一方がアルキル基又はアリール基であり、Ｒ３３はアルキル基又はアリール基を表し、Ｒ３１又はＲ３２と、Ｒ３３とが連結して環状エーテルを形成してもよい。Ｒ３４は水素原子又はメチル基を表し、Ｘ０は単結合又はアリーレン基を表す。 In general formula A, R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group. Alternatively, it represents an aryl group, and R 31 or R 32 and R 33 may be linked to form a cyclic ether. R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or an arylene group.
　　特許文献１：特開２０１５－１８７６３４号公報
　　特許文献２：特開２０１１－３９２６６号公報
　　特許文献３：特開２０１７－１５６７３５号公報 Patent Document 1: Japanese Patent Laid-Open No. 2015-187634 Patent Document 2: Japanese Patent Laid-Open No. 2011-39266 Patent Document 3: Japanese Patent Laid-Open No. 2017-156735
　本発明の一実施形態が解決しようとする課題は、ラミネート適性、及び、解像性に優れる感光性転写材料を提供することである。
　また、本発明の他の一実施形態が解決しようとする課題は、上記感光性転写材料を用いた樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法を提供することである。 The problem to be solved by an embodiment of the present invention is to provide a photosensitive transfer material having excellent laminating properties and resolution.
Another problem to be solved by another embodiment of the present invention is to provide a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method using the photosensitive transfer material. .
　上記課題を解決するための手段には、以下の態様が含まれる。
＜１＞　仮支持体と、感光性樹脂層とを有し、上記感光性樹脂層が、下記ａ１及びａ２の少なくとも一方を満たす重合体成分、並びに、光酸発生剤を含み、上記重合体成分のガラス転移温度が、９０℃以下である感光性転写材料。
　ａ１：酸分解性基で保護された酸基を有する構成単位、及び、ｐＫａＨが３以上の基を有する構成単位を有する重合体を含む重合体成分
　ａ２：酸分解性基で保護された酸基を有する構成単位を有する重合体、及び、ｐＫａＨが３以上の基を有する構成単位を有する重合体を含む重合体成分
＜２＞　上記感光性樹脂層中に含まれる全てのｐＫａＨが３以上の基のうち、上記重合体成分に含まれるｐＫａＨが３以上の基の割合が、３０モル％以上である＜１＞に記載の感光性転写材料。
＜３＞　上記感光性樹脂層中に含まれる全てのｐＫａＨが３以上の基のうち、上記重合体成分に含まれるｐＫａＨが３以上の基の割合が、５０モル％以上である＜１＞又は＜２＞に記載の感光性転写材料。
＜４＞　上記重合体成分における重合体が、酸分解性基で保護された酸基を有する構成単位及びｐＫａＨが３以上の基を有する構成単位以外の構成単位を更に有する＜１＞～＜３＞のいずれか１つに記載の感光性転写材料。
＜５＞　上記ｐＫａＨが３以上の基を有する構成単位が、下記式Ｉ又は式ＩＩで表される構成単位である＜１＞～＜４＞のいずれか１つに記載の感光性転写材料。 Means for solving the above problems include the following aspects.
<1> A temporary support and a photosensitive resin layer, wherein the photosensitive resin layer includes a polymer component satisfying at least one of the following a1 and a2, and a photoacid generator, and the polymer component The photosensitive transfer material whose glass transition temperature is 90 degrees C or less.
a1: Polymer component containing a structural unit having an acid group protected by an acid-decomposable group and a polymer having a structural unit having a pKaH group of 3 or more a2: An acid group protected by an acid-decomposable group And a polymer component comprising a polymer having a structural unit having a structural unit having a pKaH group of 3 or more <2> All pKaH groups contained in the photosensitive resin layer are 3 or more groups Among these, the photosensitive transfer material as described in <1> whose ratio of the group whose pKaH is 3 or more contained in the polymer component is 30 mol% or more.
<3> Of all the groups having 3 or more pKaH contained in the photosensitive resin layer, the ratio of the group having 3 or more pKaH contained in the polymer component is 50 mol% or more <1> or The photosensitive transfer material as described in <2>.
<4> The polymer in the polymer component further includes a structural unit other than a structural unit having an acid group protected by an acid-decomposable group and a structural unit having a pKaH of 3 or more. <1> to <3 > The photosensitive transfer material as described in any one of>.
<5> The photosensitive transfer material according to any one of <1> to <4>, wherein the structural unit having the pKaH group of 3 or more is a structural unit represented by the following formula I or formula II.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式Ｉ及び式ＩＩ中、Ｒ１は水素原子又はメチル基を表し、Ｚは単結合、メチレン基、アリーレン基、－Ｏ－、－Ｃ（＝Ｏ）－ＮＨ－又は－Ｃ（＝Ｏ）－Ｏ－を表し、Ｒ２は単結合、又は、エーテル結合、ウレタン結合、ウレア結合、アミド結合、エステル結合及びカーボネート結合よりなる群から選ばれた少なくとも１種の基を有していてもよい炭素数１～１０の直鎖状、分岐状若しくは環状のアルキレン基を表し、Ｒ３及びＲ４はそれぞれ独立に、水素原子、又は、エーテル結合、チオエーテル結合、ヒドロキシ基、ホルミル基、アセトキシ基、シアノ基、ウレタン結合、ウレア結合、アミド結合、エステル結合、カーボネート結合及び芳香族基よりなる群から選ばれた少なくとも１種の基を有していてもよい炭素数１～２０の直鎖状、分岐状若しくは環状のアルキル基を表し、Ｒ２とＲ３、Ｒ２とＲ４、又は、Ｒ３とＲ４はそれぞれ結合して環を形成していてもよく、Ｑ１は、窒素原子を有する芳香族基又は含窒素複素芳香族基を表す。 In Formulas I and II, R 1 represents a hydrogen atom or a methyl group, and Z is a single bond, a methylene group, an arylene group, —O—, —C (═O) —NH—, or —C (═O) —. Represents O—, and R 2 may have a single bond or at least one group selected from the group consisting of an ether bond, a urethane bond, a urea bond, an amide bond, an ester bond and a carbonate bond. Represents a linear, branched or cyclic alkylene group of 1 to 10, wherein R 3 and R 4 are each independently a hydrogen atom, or an ether bond, a thioether bond, a hydroxy group, a formyl group, an acetoxy group, a cyano group A linear group having 1 to 20 carbon atoms which may have at least one group selected from the group consisting of a group, a urethane bond, a urea bond, an amide bond, an ester bond, a carbonate bond and an aromatic group, Represents a branched or cyclic alkyl group, R 2 and R 3 , R 2 and R 4 , or R 3 and R 4 may be bonded to each other to form a ring, and Q 1 represents a nitrogen atom Represents an aromatic group or a nitrogen-containing heteroaromatic group.
＜６＞　上記ｐＫａＨが３以上の基を有する構成単位が、上記式Ｉで表される構成単位である＜５＞に記載の感光性転写材料。
＜７＞　上記酸分解性基で保護された酸基を有する構成単位が、下記式Ａで表される構成単位である＜１＞～＜６＞のいずれか１つに記載の感光性転写材料。 <6> The photosensitive transfer material according to <5>, wherein the structural unit having the pKaH group of 3 or more is a structural unit represented by the formula I.
<7> The photosensitive transfer material according to any one of <1> to <6>, wherein the structural unit having an acid group protected with an acid-decomposable group is a structural unit represented by the following formula A: .
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式Ａ中、Ｒ３１及びＲ３２はそれぞれ独立に、水素原子、アルキル基又はアリール基を表し、少なくともＲ３１及びＲ３２のいずれか一方がアルキル基又はアリール基であり、Ｒ３３はアルキル基又はアリール基を表し、Ｒ３１又はＲ３２と、Ｒ３３とが連結して環状エーテルを形成してもよく、Ｒ３４は水素原子又はメチル基を表し、Ｘ０は単結合又は２価の連結基を表す。 In formula A, R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group or Represents an aryl group, and R 31 or R 32 and R 33 may combine to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or a divalent linking group. Represents.
＜８＞＜１＞～＜７＞のいずれか１つに記載の感光性転写材料における上記感光性樹脂層を基板に接触させて貼り合わせる工程と、上記感光性樹脂層をパターン露光する工程と、露光された上記感光性樹脂層を現像してパターンを形成する工程と、をこの順に含む樹脂パターンの製造方法。
＜９＞　＜１＞～＜７＞のいずれか１つに記載の感光性転写材料の上記感光性樹脂層を、導電層を有する基板に接触させて貼り合わせる工程と、上記感光性樹脂層をパターン露光する工程と、露光された上記感光性樹脂層を現像してパターンを形成する工程と、上記パターンが配置されていない領域における導電層をエッチング処理する工程と、をこの順に含む回路配線の製造方法。
＜１０＞　上記導電層が、銅を含む層である＜９＞に記載の回路配線の製造方法。
＜１１＞　＜１＞～＜７＞のいずれか１つに記載の感光性転写材料の上記感光性樹脂層を、導電層を有する基板に接触させて貼り合わせる工程と、上記感光性樹脂層をパターン露光する工程と、露光された上記感光性樹脂層を現像してパターンを形成する工程と、上記パターンが配置されていない領域における導電層をエッチング処理する工程と、をこの順に含むタッチパネルの製造方法。 <8> A step of bringing the photosensitive resin layer in the photosensitive transfer material according to any one of <1> to <7> into contact with a substrate and bonding the substrate; and a step of pattern exposing the photosensitive resin layer; And a step of developing the exposed photosensitive resin layer to form a pattern, in this order.
<9> A step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of <1> to <7> into contact with a substrate having a conductive layer and bonding the photosensitive resin layer, A circuit wiring including a pattern exposure step, a step of developing the exposed photosensitive resin layer to form a pattern, and a step of etching a conductive layer in a region where the pattern is not disposed. Production method.
<10> The method for manufacturing a circuit wiring according to <9>, wherein the conductive layer is a layer containing copper.
<11> The step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of <1> to <7> into contact with a substrate having a conductive layer and bonding the photosensitive resin layer, Manufacturing of a touch panel that includes a pattern exposure step, a step of developing the exposed photosensitive resin layer to form a pattern, and a step of etching a conductive layer in a region where the pattern is not disposed in this order. Method.
　本発明の一実施形態によれば、ラミネート適性、及び、解像性に優れる感光性転写材料を提供することができる。
　また、本発明の他の一実施形態によれば、上記感光性転写材料を用いた樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法を提供することができる。 According to one embodiment of the present invention, it is possible to provide a photosensitive transfer material that is excellent in laminating suitability and resolution.
In addition, according to another embodiment of the present invention, a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method using the photosensitive transfer material can be provided.
本開示に係る感光性転写材料の層構成の一例を示す概略図である。It is the schematic which shows an example of the laminated constitution of the photosensitive transfer material which concerns on this indication. パターンＡを示す概略図である。FIG. 6 is a schematic diagram showing a pattern A. パターンＢを示す概略図である。FIG. 6 is a schematic diagram showing a pattern B.
　以下、本開示の内容について説明する。なお、添付の図面を参照しながら説明するが、符号は省略する場合がある。
　また、本明細書において「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
　また、本明細書において、「（メタ）アクリル」はアクリル及びメタクリルの双方、又は、いずれかを表し、「（メタ）アクリレート」はアクリレート及びメタクリレートの双方、又は、いずれかを表す。
　更に、本明細書において組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する該当する複数の物質の合計量を意味する。
　本明細書において「工程」との語は、独立した工程だけでなく、他の工程と明確に区別できない場合であっても工程の所期の目的が達成されれば、本用語に含まれる。
　本明細書における基（原子団）の表記において、置換及び無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も含む。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線（活性エネルギー線）が挙げられる。
　また、本明細書における化学構造式は、水素原子を省略した簡略構造式で記載する場合もある。
　本開示において、「質量％」と「重量％」とは同義であり、「質量部」と「重量部」とは同義である。
　また、本開示において、２以上の好ましい態様の組み合わせは、より好ましい態様である。
　また、本開示における重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、特に断りのない限り、ＴＳＫｇｅｌ　ＧＭＨｘＬ、ＴＳＫｇｅｌ　Ｇ４０００ＨｘＬ、ＴＳＫｇｅｌ　Ｇ２０００ＨｘＬ（何れも東ソー（株）製の商品名）のカラムを使用したゲルパーミエーションクロマトグラフィ（ＧＰＣ）分析装置により、溶媒ＴＨＦ（テトラヒドロフラン）、示差屈折計により検出し、標準物質としてポリスチレンを用いて換算した分子量である。 Hereinafter, the contents of the present disclosure will be described. In addition, although it demonstrates referring an accompanying drawing, a code | symbol may be abbreviate | omitted.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, “(meth) acryl” represents both and / or acryl and methacryl, and “(meth) acrylate” represents both and / or acrylate and methacrylate.
Further, in the present specification, the amount of each component in the composition is the sum of the plurality of corresponding substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.
In this specification, the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
In the notation of groups (atomic groups) in this specification, the notation that does not indicate substitution and non-substitution includes those having no substituent and those having a substituent. For example, 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).
In this specification, “exposure” includes not only exposure using light, but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. In addition, as light used for exposure, in general, an emission ray spectrum of a mercury lamp, an actinic ray (active energy ray) such as a far ultraviolet ray, an extreme ultraviolet ray (EUV light) represented by an excimer laser, an X-ray, and an electron beam is used. Can be mentioned.
In addition, the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
In the present disclosure, “mass%” and “weight%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) unless otherwise specified. The molecular weight was detected by a gel permeation chromatography (GPC) analyzer using a THF (tetrahydrofuran) solvent and a differential refractometer, and converted using polystyrene as a standard substance.
（感光性転写材料）
　本開示に係る感光性転写材料は、仮支持体と、感光性樹脂層とを有し、上記感光性樹脂層が、下記ａ１及びａ２の少なくとも一方を満たす重合体成分、並びに、光酸発生剤を含み、上記重合体成分のガラス転移温度（Ｔｇ）が、９０℃以下である。
　ａ１：酸分解性基で保護された酸基を有する構成単位、及び、ｐＫａＨが３以上の基を有する構成単位を有する重合体を含む重合体成分
　ａ２：酸分解性基で保護された酸基を有する構成単位を有する重合体、及び、ｐＫａＨが３以上の基を有する構成単位を有する重合体を含む重合体成分
　また、本開示に係る感光性転写材料は、ポジ型感光性転写材料である。 (Photosensitive transfer material)
A photosensitive transfer material according to the present disclosure includes a temporary support and a photosensitive resin layer, and the photosensitive resin layer satisfies at least one of the following a1 and a2, and a photoacid generator The glass transition temperature (Tg) of the polymer component is 90 ° C. or lower.
a1: Polymer component containing a structural unit having an acid group protected by an acid-decomposable group and a polymer having a structural unit having a pKaH group of 3 or more a2: An acid group protected by an acid-decomposable group And a polymer component comprising a polymer having a structural unit having a pKaH group of 3 or more. The photosensitive transfer material according to the present disclosure is a positive photosensitive transfer material. .
　従来のポジ型感光性転写材料には、発生した酸を捕捉し酸分解性基の分解反応を停止させる目的で、低分子塩基性化合物（「クエンチャー」ともいう。）を添加する場合があった。しかしながら、従来の低分子塩基性化合物を添加した感光性転写材料では、低分子塩基性化合物が転写した基板側等に偏在しやすく、上記偏在により現像時のレジストパターン下部において裾引きが発生し、解像性が悪い場合があることを本発明者らは見出した。この課題は、Ｔｇが９０℃以下である酸分解性ポリマーと、光酸発生剤とを含む感光性転写材料に特有の課題であり、塗布型などの転写性でないＴｇが９０℃を超える高Ｔｇポリマーを用いる従来のレジスト組成物では見られない課題であった。
　本発明者らは鋭意検討を重ねた結果、上記構成の感光性転写材料とすることにより、ラミネート適性、及び、解像性に優れることを見出した。
　詳細な上記効果の発現機構は不明であるが、ｐＫａＨが３以上の基を有する構成単位を有する重合体を含有することにより、塩基成分であるｐＫａＨが３以上の基が、重合体に固定され、塩基成分であるｐＫａＨが３以上の基を有する構成単位が基板側に偏在するのを抑制し、現像時のレジストパターンの裾引きに由来する解像性の低下を改良できたものと考えている。したがって、低分子成分が移動しやすいと考えられるＴｇが９０℃以下の重合体成分を用いても、現像時のレジストパターンの裾引きに由来する解像性の低下を改良でき、また、Ｔｇが９０℃以下の重合体成分であるため、ラミネート適性も優れる。 Conventional positive photosensitive transfer materials may contain a low molecular weight basic compound (also referred to as “quencher”) for the purpose of capturing the generated acid and stopping the decomposition reaction of the acid-decomposable group. It was. However, in the photosensitive transfer material to which the conventional low molecular weight basic compound is added, the low molecular weight basic compound tends to be unevenly distributed on the transferred substrate side, etc., and the uneven distribution causes tailing at the bottom of the resist pattern during development, The present inventors have found that the resolution may be poor. This problem is specific to a photosensitive transfer material containing an acid-decomposable polymer having a Tg of 90 ° C. or less and a photoacid generator, and has a high Tg of 90 g. This is a problem that cannot be seen in conventional resist compositions using polymers.
As a result of intensive studies, the present inventors have found that by using the photosensitive transfer material having the above-described structure, the laminate suitability and the resolution are excellent.
The detailed expression mechanism of the above effect is unknown, but by containing a polymer having a structural unit having pKaH of 3 or more groups, a group having a basic component of pKaH of 3 or more is fixed to the polymer. It is considered that the structural unit having a base component of pKaH having a group of 3 or more is prevented from being unevenly distributed on the substrate side, and the reduction in resolution resulting from the tailing of the resist pattern during development has been improved. Yes. Therefore, even when using a polymer component having a Tg of 90 ° C. or less, which is considered to easily move the low molecular component, it is possible to improve the decrease in resolution resulting from the tailing of the resist pattern during development. Since it is a polymer component of 90 ° C. or less, the suitability for lamination is also excellent.
　また、本開示に係る感光性転写材料は、上記構成であることにより、光酸発生剤より発生する酸の余分な拡散を抑制が可能であり、感光性転写材料を露光後、ある程度時間が経過した後に現像を行った場合であっても得られる樹脂パターンの線幅の細り等を抑制できる（「引き置き時間依存抑制性」ともいう。）。 In addition, the photosensitive transfer material according to the present disclosure has the above-described configuration, so that excessive diffusion of acid generated from the photoacid generator can be suppressed, and a certain amount of time has elapsed after the photosensitive transfer material is exposed. Even when the development is performed after this, it is possible to suppress the thinning of the line width of the obtained resin pattern (also referred to as “retention time-dependent suppression”).
　以下、本開示に係る感光性転写材料について、詳細に説明する。 Hereinafter, the photosensitive transfer material according to the present disclosure will be described in detail.
　図１は、本開示に係る感光性転写材料の層構成の一例を概略的に示している。図１に示す感光性転写材料１００は、仮支持体１０と、感光性樹脂層１２と、カバーフィルム１４とがこの順に積層されている。
　感光性樹脂層１２は、上記ａ１及びａ２の少なくとも一方を満たす重合体成分、並びに、光酸発生剤を含み、上記重合体成分のガラス転移温度が、９０℃以下である。
　以下、本開示に係る感光性転写材料の構成材料等について説明する。 FIG. 1 schematically illustrates an example of a layer configuration of a photosensitive transfer material according to the present disclosure. In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 10, a photosensitive resin layer 12, and a cover film 14 are laminated in this order.
The photosensitive resin layer 12 includes a polymer component satisfying at least one of the a1 and a2 and a photoacid generator, and the glass transition temperature of the polymer component is 90 ° C. or lower.
Hereinafter, constituent materials and the like of the photosensitive transfer material according to the present disclosure will be described.
＜仮支持体＞
　仮支持体は、感光性樹脂層を支持し、剥離可能な支持体である。
　本開示に用いられる仮支持体は、感光性樹脂層をパターン露光する際に仮支持体を介して感光性樹脂層を露光し得る観点から光透過性を有することが好ましい。
　本開示において、光透過性を有するとは、パターン露光に使用する光の主波長の透過率が５０％以上であることを意味し、パターン露光に使用する光の主波長の透過率は、露光感度向上の観点から、６０％以上が好ましく、７０％以上がより好ましい。透過率の測定方法としては、大塚電子（株）製ＭＣＰＤ　Ｓｅｒｉｅｓを用いて測定する方法が挙げられる。
　仮支持体としては、ガラス基板、樹脂フィルム、紙等が挙げられ、強度及び可撓性等の観点から、樹脂フィルムが特に好ましい。樹脂フィルムとしては、ポリエチレンテレフタレートフィルム、トリ酢酸セルロースフィルム、ポリスチレンフィルム、ポリカーボネートフィルム等が挙げられる。中でも、２軸延伸ポリエチレンテレフタレートフィルムが特に好ましい。 <Temporary support>
The temporary support is a support that supports the photosensitive resin layer and can be peeled off.
The temporary support used in the present disclosure preferably has light transparency from the viewpoint that the photosensitive resin layer can be exposed through the temporary support when the photosensitive resin layer is subjected to pattern exposure.
In the present disclosure, having light transmittance means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of light used for pattern exposure is exposure. From the viewpoint of improving sensitivity, 60% or more is preferable, and 70% or more is more preferable. Examples of the method for measuring the transmittance include a method of measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
Examples of the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is particularly preferable from the viewpoints of strength and flexibility. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a biaxially stretched polyethylene terephthalate film is particularly preferable.
　仮支持体の厚みは、特に限定されず、５μｍ～２００μｍの範囲が好ましく、取扱い易さ、汎用性などの点で、１０μｍ～１５０μｍの範囲がより好ましい。
　仮支持体の厚みは、支持体としての強度、配線形成用基板との貼り合わせに求められる可撓性、最初の露光工程で要求される光透過性などの観点から、材質に応じて選択すればよい。 The thickness of the temporary support is not particularly limited, but is preferably in the range of 5 μm to 200 μm, and more preferably in the range of 10 μm to 150 μm from the viewpoint of ease of handling and versatility.
The thickness of the temporary support is selected according to the material from the viewpoints of strength as a support, flexibility required for bonding with a wiring forming substrate, light transmittance required in the first exposure process, and the like. That's fine.
　仮支持体の好ましい態様については、例えば、特開２０１４－８５６４３号公報の段落００１７～段落００１８に記載があり、この公報の内容は本明細書に組み込まれる。 A preferred embodiment of the temporary support is described, for example, in paragraphs 0017 to 0018 of JP-A-2014-85643, and the contents of this publication are incorporated in this specification.
＜感光性樹脂層＞
　本開示に係る感光性転写材料は、仮支持体、及び、感光性樹脂層を少なくとも有し、上記感光性樹脂層が、上記ａ１及びａ２の少なくとも一方を満たす重合体成分、並びに、光酸発生剤を含み、上記重合体成分のガラス転移温度（Ｔｇ）が、９０℃以下である。
　上記感光性樹脂層は、化学増幅ポジ型感光性樹脂層であることが好ましい。
　後述するオニウム塩やオキシムスルホネート化合物等の光酸発生剤は、活性光線に感応して生成される酸が、酸分解性で保護された酸基を有するバインダー中の保護された酸基の脱保護に対して触媒として作用するので、１個の光量子の作用で生成した酸が、多数の脱保護反応に寄与し、量子収率は１を超え、例えば、１０の数乗のような大きい値となり、いわゆる化学増幅の結果として、高感度が得られる。
　一方、活性光線に感応する光酸発生剤としてキノンジアジド化合物（ＮＱＤ）を用いた場合、逐次型光化学反応によりカルボキシ基を生成するが、その量子収率は必ず１以下であり、化学増幅型には該当しない。 <Photosensitive resin layer>
The photosensitive transfer material according to the present disclosure has at least a temporary support and a photosensitive resin layer, and the photosensitive resin layer satisfies at least one of the a1 and a2, and a photoacid generator. The glass transition temperature (Tg) of the polymer component is 90 ° C. or less.
The photosensitive resin layer is preferably a chemically amplified positive photosensitive resin layer.
Photoacid generators such as onium salts and oxime sulfonate compounds described below are used to deprotect protected acid groups in binders in which the acid generated in response to actinic rays has acid-decomposable and protected acid groups. The acid produced by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as the power of 10 High sensitivity is obtained as a result of so-called chemical amplification.
On the other hand, when a quinonediazide compound (NQD) is used as a photoacid generator sensitive to actinic rays, a carboxy group is generated by a sequential photochemical reaction, but its quantum yield is always 1 or less. Not applicable.
＜＜重合体成分＞＞
　上記感光性樹脂層に含まれる重合体成分は、下記ａ１及びａ２の少なくとも一方を満たす。また、上記重合体成分のガラス転移温度は、９０℃以下である。
　ａ１：酸分解性基で保護された酸基を有する構成単位、及び、ｐＫａＨが３以上の基を有する構成単位を有する重合体を含む重合体成分
　ａ２：酸分解性基で保護された酸基を有する構成単位を有する重合体、及び、ｐＫａＨが３以上の基を有する構成単位を有する重合体を含む重合体成分 << polymer component >>
The polymer component contained in the photosensitive resin layer satisfies at least one of the following a1 and a2. Moreover, the glass transition temperature of the said polymer component is 90 degrees C or less.
a1: Polymer component containing a structural unit having an acid group protected by an acid-decomposable group and a polymer having a structural unit having a pKaH group of 3 or more a2: An acid group protected by an acid-decomposable group And a polymer component comprising a polymer having a structural unit having pKaH and a structural unit having a structural unit having 3 or more groups
　上記重合体成分は、現像性の観点からは、上記ａ１を満たすことが好ましく、物性調整の容易性の観点からは、上記ａ２を満たすことが好ましい。
　また、上記重合体成分に含まれる全ての重合体がそれぞれ、酸分解性基で保護された酸基を有する構成単位及び酸基を有する構成単位よりなる群から選ばれた少なくとも１種の構成単位を有する重合体であることが好ましい。
　上記ａ１及びａ２に示す各重合体はそれぞれ、１種のみ含んでいても、２種以上含んでいてもよい。
　また、上記重合体成分は、更に、上記ａ１及びａ２に示す重合体以外の重合体を含んでいてもよい。
　本開示における重合体成分は、特に述べない限り、上記ａ１又はａ２の態様に加え、必要に応じて添加される他の重合体を含めたものを意味するものとする。 The polymer component preferably satisfies the above a1 from the viewpoint of developability, and preferably satisfies the above a2 from the viewpoint of easy physical property adjustment.
Further, all the polymers contained in the polymer component are each at least one structural unit selected from the group consisting of a structural unit having an acid group protected with an acid-decomposable group and a structural unit having an acid group. It is preferable that it is a polymer which has.
Each of the polymers shown in a1 and a2 may contain only one type or two or more types.
Moreover, the polymer component may further contain a polymer other than the polymers shown in the a1 and a2.
Unless otherwise specified, the polymer component in the present disclosure means one including other polymers added as necessary in addition to the above-described aspect of a1 or a2.
　上記重合体成分における重合体は、付加重合型の樹脂であることが好ましく、（メタ）アクリル酸及び／若しくはそのエステルに由来する構成単位、並びに／又は、スチレン化合物及び／若しくはビニルナフタレン化合物に由来する構成単位を含む重合体であることがより好ましく、（メタ）アクリル酸及び／又はそのエステルに由来する構成単位を含む重合体であることが更に好ましい。なお、上記以外の構成単位、例えば、ビニル化合物に由来する構成単位等を有していてもよい。 The polymer in the polymer component is preferably an addition polymerization type resin, and is derived from a structural unit derived from (meth) acrylic acid and / or an ester thereof, and / or a styrene compound and / or a vinyl naphthalene compound. It is more preferable that the polymer contains a structural unit, and a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof is more preferable. In addition, you may have structural units other than the above, for example, a structural unit derived from a vinyl compound.
－重合体成分のガラス転移温度（Ｔｇ）－
　本開示における上記重合体成分のガラス転移温度（Ｔｇ）は、９０℃以下であり、６０℃以下であることが好ましく、５０℃以下であることがより好ましい。上記範囲であると、上記感光性樹脂層は高い密着性を有し、転写性に優れる。
　また、上記Ｔｇの下限値には特に制限はないが、－２０℃以上が好ましく、－１０℃以上がより好ましく、１０℃以上であることが更に好ましく、２５℃以上であることが特に好ましい。重合体成分のＴｇが－２０℃以上であることで、良好なパターン形成性が維持され、また、例えば、カバーフィルムを用いる場合、カバーフィルムを剥離する際の剥離故障が抑制される。
　更に、本開示における酸分解性基で保護された酸基を有する構成単位、及び、ｐＫａＨが３以上の基を有する構成単位を有する重合体、酸分解性基で保護された酸基を有する構成単位を有する重合体、又は、ｐＫａＨが３以上の基を有する構成単位を有する重合体のガラス転移温度（Ｔｇ）はそれぞれ独立に、転写性の観点から、９０℃以下であることが好ましく、－２０℃以上７０℃以下であることがより好ましく、１０℃以上６０℃以下であることが更に好ましく、２５℃以上５０℃以下であることが特に好ましい。 -Glass transition temperature (Tg) of polymer component-
The glass transition temperature (Tg) of the polymer component in the present disclosure is 90 ° C. or lower, preferably 60 ° C. or lower, and more preferably 50 ° C. or lower. Within the above range, the photosensitive resin layer has high adhesion and excellent transferability.
The lower limit of Tg is not particularly limited, but is preferably −20 ° C. or higher, more preferably −10 ° C. or higher, still more preferably 10 ° C. or higher, and particularly preferably 25 ° C. or higher. When the Tg of the polymer component is −20 ° C. or higher, good pattern formability is maintained, and when a cover film is used, for example, peeling failure when peeling the cover film is suppressed.
Further, in the present disclosure, a structural unit having an acid group protected with an acid-decomposable group, a polymer having a structural unit having a pKaH group of 3 or more, and a structure having an acid group protected by an acid-decomposable group The glass transition temperature (Tg) of the polymer having a unit or the polymer having a structural unit having a pKaH group of 3 or more is preferably 90 ° C. or less independently from the viewpoint of transferability. It is more preferably 20 ° C. or higher and 70 ° C. or lower, further preferably 10 ° C. or higher and 60 ° C. or lower, and particularly preferably 25 ° C. or higher and 50 ° C. or lower.
　重合体のガラス転移温度は、示差走査熱量測定（ＤＳＣ）を用いて測定することができる。
　具体的な測定方法は、ＪＩＳ　Ｋ　７１２１（１９８７年）に記載の方法に順じて行う。本明細書におけるガラス転移温度は、補外ガラス転移開始温度（以下、Ｔｉｇと称することがある。）を用いる。
　ガラス転移温度の測定方法をより具体的に説明する。
　ガラス転移温度を求める場合、予想される重合体のＴｇより約５０℃低い温度にて装置が安定するまで保持した後、加熱速度：２０℃／分で、ガラス転移が終了した温度よりも約３０℃高い温度まで加熱し、ＤＴＡ曲線又はＤＳＣ曲線を描かせる。
　補外ガラス転移開始温度（Ｔｉｇ）、すなわち、本明細書におけるガラス転移温度Ｔｇは、ＤＴＡ曲線又はＤＳＣ曲線における低温側のベースラインを高温側に延長した直線と、ガラス転移の階段状変化部分の曲線の勾配が最大になる点で引いた接線との交点の温度として求める。 The glass transition temperature of the polymer can be measured using differential scanning calorimetry (DSC).
A specific measuring method is performed in accordance with the method described in JIS K 7121 (1987). As the glass transition temperature in this specification, an extrapolated glass transition start temperature (hereinafter sometimes referred to as Tig) is used.
The method for measuring the glass transition temperature will be described more specifically.
When determining the glass transition temperature, after maintaining the apparatus at a temperature about 50 ° C. lower than the expected Tg of the polymer until the apparatus is stabilized, the heating rate is about 20 ° C./min and about 30 times higher than the temperature at which the glass transition is completed. Heat to a higher temperature and draw a DTA or DSC curve.
The extrapolated glass transition start temperature (Tig), that is, the glass transition temperature Tg in the present specification, is a straight line obtained by extending the low-temperature side baseline in the DTA curve or DSC curve to the high-temperature side, and the step-like change portion of the glass transition. Calculated as the temperature of the intersection with the tangent drawn at the point where the slope of the curve is maximum.
　重合体のＴｇを、既述の好ましい範囲に調整する方法としては、例えば、目的とする重合体の各構成単位の単独重合体のＴｇと各構成単位の質量比より、ＦＯＸ式を指針にして、目的とする重合体のＴｇを制御することが可能である。
　ＦＯＸ式について
　重合体に含まれる第１の構成単位の単独重合体のＴｇをＴｇ１、第１の構成単位の共重合体における質量分率をＷ１とし、第２の構成単位の単独重合体のＴｇをＴｇ２とし、第２の構成単位の共重合体における質量分率をＷ２としたときに、第１の構成単位と第２の構成単位とを含む共重合体のＴｇ０（Ｋ）は、以下の式にしたがって推定することが可能である。
　ＦＯＸ式：１／Ｔｇ０＝（Ｗ１／Ｔｇ１）＋（Ｗ２／Ｔｇ２）
　既述のＦＯＸ式を用いて、共重合体に含まれる各構成単位の種類と質量分率を調整して、所望のＴｇを有する共重合体を得ることができる。
　また、重合体の重量平均分子量を調整することにより、重合体のＴｇを調整することも可能である。 As a method for adjusting the Tg of the polymer to the above-described preferable range, for example, from the Tg of the homopolymer of each constituent unit of the target polymer and the mass ratio of each constituent unit, the FOX formula is used as a guideline. It is possible to control the Tg of the target polymer.
Regarding the FOX formula: Tg of the homopolymer of the first structural unit contained in the polymer is Tg1, the mass fraction in the copolymer of the first structural unit is W1, and the Tg of the homopolymer of the second structural unit Is Tg2 and the mass fraction in the copolymer of the second structural unit is W2, the Tg0 (K) of the copolymer containing the first structural unit and the second structural unit is It is possible to estimate according to the equation.
FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)
A copolymer having a desired Tg can be obtained by adjusting the type and mass fraction of each structural unit contained in the copolymer using the FOX formula described above.
It is also possible to adjust the Tg of the polymer by adjusting the weight average molecular weight of the polymer.
　また、本開示における重合体成分のガラス転移温度は、重合体成分に含まれる各重合体のガラス転移温度を測定又は算出し、加重平均、すなわち、各重合体のガラス転移温度と重合体成分全体に対する質量比との積を足し合わせることにより、求めるものとする。
　重合体成分のＴｇ＝重合体１のＴｇ×重合体１の含有割合＋重合体２のＴｇ×重合体２の含有割合＋・・・ Further, the glass transition temperature of the polymer component in the present disclosure is obtained by measuring or calculating the glass transition temperature of each polymer contained in the polymer component, and the weighted average, that is, the glass transition temperature of each polymer and the entire polymer component. It shall be obtained by adding the product of the mass ratio to.
Tg of polymer component = Tg of polymer 1 × content ratio of polymer 1 + Tg of polymer 2 × content ratio of polymer 2+...
－重合体の重量平均分子量（Ｍｗ）－
　重合体の重量平均分子量（Ｍｗ）は、ラミネート適性の観点から、ポリスチレン換算重量平均分子量で、６０，０００以下であることが好ましく、２，０００～６０，０００であることがより好ましく、３，０００～５０，０００であることが更に好ましく、１５，０００～５０，０００であることが特に好ましい。
　なお、重合体の重量平均分子量及び数平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によって測定することができ、測定装置としては、様々な市販の装置を用いることができ、装置の内容、及び、測定技術は当業者に公知である。
　ゲルパーミエーションクロマトグラフィ（ＧＰＣ）による重量平均分子量の測定は、測定装置として、ＨＬＣ（登録商標）－８２２０ＧＰＣ（東ソー（株）製）を用い、カラムとして、ＴＳＫｇｅｌ（登録商標）Ｓｕｐｅｒ　ＨＺＭ－Ｍ（４．６ｍｍＩＤ×１５ｃｍ、東ソー（株）製）、Ｓｕｐｅｒ　ＨＺ４０００（４．６ｍｍＩＤ×１５ｃｍ、東ソー（株）製）、Ｓｕｐｅｒ　ＨＺ３０００（４．６ｍｍＩＤ×１５ｃｍ、東ソー（株）製）、Ｓｕｐｅｒ　ＨＺ２０００（４．６ｍｍＩＤ×１５ｃｍ、東ソー（株）製）をそれぞれ１本、直列に連結したものを用い、溶離液として、ＴＨＦ（テトラヒドロフラン）を用いることができる。
　また、測定条件としては、試料濃度を０．２質量％、流速を０．３５ｍｌ／ｍｉｎ、サンプル注入量を１０μｌ、及び測定温度を４０℃とし、示差屈折率（ＲＩ）検出器を用いて行うことができる。
　検量線は、東ソー（株）製の「標準試料ＴＳＫ　ｓｔａｎｄａｒｄ，ｐｏｌｙｓｔｙｒｅｎｅ」：「Ｆ－４０」、「Ｆ－２０」、「Ｆ－４」、「Ｆ－１」、「Ａ－５０００」、「Ａ－２５００」及び「Ａ－１０００」の７サンプルのいずれかのサンプルを少なくとも２つ以上用いて作製できる。 -Weight average molecular weight of polymer (Mw)-
The weight average molecular weight (Mw) of the polymer is preferably 60,000 or less, more preferably 2,000 to 60,000 in terms of polystyrene, from the viewpoint of laminate suitability, More preferably, it is 000 to 50,000, and particularly preferably 15,000 to 50,000.
In addition, the weight average molecular weight and number average molecular weight of the polymer can be measured by GPC (gel permeation chromatography), and various commercially available apparatuses can be used as the measuring apparatus, and the contents of the apparatus, and Measurement techniques are known to those skilled in the art.
For the measurement of the weight average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark) -8220GPC (manufactured by Tosoh Corporation) was used as a measuring device, and TSKgel (registered trademark) Super HZM-M (4 .6 mm ID × 15 cm, manufactured by Tosoh Corporation), Super HZ4000 (4.6 mm ID × 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mm ID × 15 cm, manufactured by Tosoh Corporation), Super HZ2000 (4.6 mm ID) × 15 cm, manufactured by Tosoh Corp.), each connected in series, and THF (tetrahydrofuran) can be used as an eluent.
Measurement conditions are 0.2% by mass, flow rate is 0.35 ml / min, sample injection amount is 10 μl, measurement temperature is 40 ° C., and a differential refractive index (RI) detector is used. be able to.
The calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “ It can be produced using at least two of any of the seven samples of “A-2500” and “A-1000”.
　重合体の数平均分子量と重量平均分子量との比（分散度）は、１．０～５．０が好ましく、１．０５～３．５がより好ましい。 The ratio (dispersion degree) between the number average molecular weight and the weight average molecular weight of the polymer is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.
－ｐＫａＨが３以上の基を有する構成単位－
　上記重合体成分は、ｐＫａＨが３以上の基を有する構成単位を少なくとも有する重合体を含む。
　具体的には、例えば、酸分解性基で保護された酸基を有する構成単位、及び、ｐＫａＨが３以上の基を有する構成単位を有する重合体、又は、酸分解性基で保護された酸基を有する構成単位を有さず、かつｐＫａＨが３以上の基を有する構成単位を有する重合体が挙げられる。
　本開示におけるｐＫａＨは、共役酸のｐＫａであり、ｐＫａＨが３以上の基とは、その基の共役酸のｐＫａが３以上である基を表す。例えば、－ＮＨ２のｐＫａＨの値は、－ＮＨ３ ＋のｐＫａの値である。
　また、本開示において、ｐＫａＨは、ACD/ChemSketch（ACD/Labs 8.00 Release Product Version:8.08）により求めた計算値である。
　具体的には、特定の官能基を有する構成単位の化学構造から、上記ACD/ChemSketchを用いて計算し、特定の官能基のｐＫａＨの値を算出する。 -Constitutional unit in which pKaH has 3 or more groups-
The polymer component includes a polymer having at least a structural unit having a pKaH of 3 or more.
Specifically, for example, a polymer having a structural unit having an acid group protected by an acid-decomposable group and a structural unit having a pKaH group of 3 or more, or an acid protected by an acid-decomposable group Examples thereof include a polymer having no structural unit having a group and having a structural unit having a pKaH of 3 or more.
In the present disclosure, pKaH is a pKa of a conjugate acid, and a group having a pKaH of 3 or more represents a group having a pKa of a conjugate acid of the group of 3 or more. For example, the value of pKaH of —NH 2 is the value of pKa of —NH 3 + .
In the present disclosure, pKaH is a calculated value obtained by ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08).
Specifically, from the chemical structure of the structural unit having a specific functional group, the above-mentioned ACD / ChemSketch is used to calculate the pKaH value of the specific functional group.
　上記ｐＫａＨが３以上の基は、解像性及び引き置き時間依存抑制性の観点から、ｐＫａＨが４以上の基であることが好ましく、ｐＫａＨが５以上の基であることがより好ましく、ｐＫａＨが５以上１５以下の基であることが更に好ましく、ｐＫａＨが６以上１０以下の基であることが特に好ましい。
　また、言い換えると、上記重合体成分は、解像性及び引き置き時間依存抑制性の観点から、ｐＫａＨが４以上の基を有する構成単位を少なくとも有する重合体を含むことが好ましく、ｐＫａＨが５以上の基を有する構成単位を少なくとも有する重合体を含むことがより好ましく、ｐＫａＨが５以上１５以下の基を有する構成単位を少なくとも有する重合体を含むことが更に好ましく、ｐＫａＨが６以上１０以下の基を有する構成単位を少なくとも有する重合体を含むことが特に好ましい。 The group having a pKaH of 3 or more is preferably a group having a pKaH of 4 or more, more preferably a group having a pKaH of 5 or more, from the viewpoints of resolution and retention time-dependent suppression. A group of 5 or more and 15 or less is more preferable, and a group having a pKaH of 6 or more and 10 or less is particularly preferable.
In other words, the polymer component preferably includes a polymer having at least a constituent unit having a pKaH group of 4 or more, and a pKaH of 5 or more, from the viewpoint of resolution and retention time-dependent suppression. It is more preferable to include a polymer having at least a structural unit having a group, and it is further preferable to include a polymer having at least a structural unit having a pKaH of 5 or more and 15 or less, and a group having a pKaH of 6 to 10 or less. It is particularly preferable to include a polymer having at least a structural unit having.
　上記ｐＫａＨが３以上の基としては、解像性及び引き置き時間依存抑制性の観点から、窒素原子を有する基であることが好ましく、脂肪族アミノ基、芳香族アミノ基、又は、含窒素複素芳香環基であることがより好ましく、脂肪族アミノ基、又は、含窒素複素芳香環基であることが更に好ましく、脂肪族アミノ基が特に好ましい。
　脂肪族アミノ基としては、第一級アミノ基、第二級アミノ基、又は、第三級アミノ基のいずれであってもよいが、解像性及び引き置き時間依存抑制性の観点から、第二級アミノ基、又は、第三級アミノ基であることが好ましい。
　芳香族アミノ基としては、アニリノ基、モノアルキルアニリノ基、又は、ジアルキルアニリノ基であることが好ましく、モノアルキルアニリノ基、又は、ジアルキルアニリノ基であることがより好ましい。
　含窒素複素芳香環基における含窒素複素芳香環としては、ピリジン環、イミダゾール環、又は、トリアゾール環であることが好ましく、ピリジン環、又は、イミダゾール環であることがより好ましく、ピリジン環であることが特に好ましい。
　また、上記含窒素複素芳香環基は、含窒素複素芳香環上に更に置換基を有していてもよい。上記置換基としては、特に制限はないが、アルキル基であることが好ましく、メチル基であることがより好ましい。 The group having a pKaH of 3 or more is preferably a group having a nitrogen atom from the viewpoint of resolution and retention time-dependent suppression, and is an aliphatic amino group, an aromatic amino group, or a nitrogen-containing complex. It is more preferably an aromatic ring group, further preferably an aliphatic amino group or a nitrogen-containing heteroaromatic ring group, and particularly preferably an aliphatic amino group.
The aliphatic amino group may be any of a primary amino group, a secondary amino group, or a tertiary amino group, but from the viewpoints of resolution and retention time dependence suppression, It is preferably a secondary amino group or a tertiary amino group.
The aromatic amino group is preferably an anilino group, a monoalkylanilino group, or a dialkylanilino group, and more preferably a monoalkylanilino group or a dialkylanilino group.
The nitrogen-containing heteroaromatic ring in the nitrogen-containing heteroaromatic group is preferably a pyridine ring, an imidazole ring or a triazole ring, more preferably a pyridine ring or an imidazole ring, and a pyridine ring. Is particularly preferred.
The nitrogen-containing heteroaromatic group may further have a substituent on the nitrogen-containing heteroaromatic ring. The substituent is not particularly limited, but is preferably an alkyl group, and more preferably a methyl group.
　また、上記ｐＫａＨが３以上の基としては、解像性及び引き置き時間依存抑制性の観点から、アルキルアミン構造を有する基であることが特に好ましい。
　アルキルアミン構造としては、例えば、ジアルキルアミン、トリアルキルアミンが挙げられ、具体的には、ジメチルアミノ基、ジエチルアミノ基、ジプロピルアミノ基、ジイソプロピルアミノ基、１，２，２，６，６－ペンタアルキル－４－ピぺリジル基、２，２，６，６－テトラアルキル－４－ピぺリジル基等が挙げられる。 In addition, the group having a pKaH of 3 or more is particularly preferably a group having an alkylamine structure from the viewpoint of resolution and retention time-dependent suppression.
Examples of the alkylamine structure include dialkylamine and trialkylamine. Specifically, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, 1,2,2,6,6-penta Examples include an alkyl-4-piperidyl group and a 2,2,6,6-tetraalkyl-4-piperidyl group.
　上記ｐＫａＨが３以上の基を有する構成単位は、解像性及び引き置き時間依存抑制性の観点から、下記式Ｉ又は式ＩＩで表される構成単位であることが好ましく、下記式Ｉで表される構成単位であることがより好ましい。 The structural unit having a pKaH group of 3 or more is preferably a structural unit represented by the following formula I or formula II from the viewpoints of resolution and retention time-dependent inhibition properties. More preferably, it is a structural unit.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　式Ｉ及び式ＩＩ中、Ｒ１は水素原子又はメチル基を表し、Ｚは単結合、メチレン基、アリーレン基、－Ｏ－、－Ｃ（＝Ｏ）－ＮＨ－又は－Ｃ（＝Ｏ）－Ｏ－を表し、Ｒ２は単結合、又は、エーテル結合、ウレタン結合、ウレア結合、アミド結合、エステル結合及びカーボネート結合よりなる群から選ばれた少なくとも１種の基を有していてもよい炭素数１～１０の直鎖状、分岐状若しくは環状のアルキレン基を表し、Ｒ３及びＲ４はそれぞれ独立に、水素原子、又は、エーテル結合、チオエーテル結合、ヒドロキシ基、ホルミル基、アセトキシ基、シアノ基、ウレタン結合、ウレア結合、アミド結合、エステル結合、カーボネート結合、及び芳香族基よりなる群から選ばれた少なくとも１種の基を有していてもよい炭素数１～２０の直鎖状、分岐状若しくは環状のアルキル基を表し、Ｒ２とＲ３、Ｒ２とＲ４、又は、Ｒ３とＲ４はそれぞれ結合して環を形成していてもよく、Ｑ１は、窒素原子を有する芳香族基又は含窒素複素芳香族基を表す。 In Formulas I and II, R 1 represents a hydrogen atom or a methyl group, and Z represents a single bond, a methylene group, an arylene group, —O—, —C (═O) —NH—, or —C (═O) —. Represents O—, and R 2 may have a single bond or at least one group selected from the group consisting of an ether bond, a urethane bond, a urea bond, an amide bond, an ester bond and a carbonate bond. Represents a linear, branched or cyclic alkylene group of 1 to 10, wherein R 3 and R 4 are each independently a hydrogen atom, or an ether bond, a thioether bond, a hydroxy group, a formyl group, an acetoxy group, a cyano group A linear group having 1 to 20 carbon atoms which may have at least one group selected from the group consisting of a group, a urethane bond, a urea bond, an amide bond, an ester bond, a carbonate bond, and an aromatic group Represents a branched or cyclic alkyl group, R 2 and R 3 , R 2 and R 4 , or R 3 and R 4 may be bonded to each other to form a ring, and Q 1 is a nitrogen atom Represents an aromatic group having nitrogen or a nitrogen-containing heteroaromatic group.
　式ＩにおけるＺは、解像性、引き置き時間依存抑制性及び合成容易性の観点から、単結合、アリーレン基、－Ｃ（＝Ｏ）－ＮＨ－又は－Ｃ（＝Ｏ）－Ｏ－であることが好ましく、アリーレン基、－Ｃ（＝Ｏ）－ＮＨ－又は－Ｃ（＝Ｏ）－Ｏ－であることがより好ましく、－Ｃ（＝Ｏ）－ＮＨ－又は－Ｃ（＝Ｏ）－Ｏ－であることが特に好ましい。
　式ＩＩにおけるＺは、解像性、引き置き時間依存抑制性及び合成容易性の観点から、単結合、アリーレン基又は－Ｃ（＝Ｏ）－Ｏ－であることが好ましく、単結合であることがより好ましい。
　式ＩにおけるＲ２は、解像性、引き置き時間依存抑制性及び合成容易性の観点から、エーテル結合、ウレタン結合及びウレア結合よりなる群から選ばれた少なくとも１種の基を有していてもよい炭素数１～１０の直鎖状、分岐状若しくは環状のアルキレン基であることが好ましく、エーテル結合、ウレタン結合及びウレア結合よりなる群から選ばれた少なくとも１種の基を有していてもよい炭素数２～１０の直鎖状、分岐状若しくは環状のアルキレン基であることがより好ましく、炭素数２～１０の直鎖状、分岐状若しくは環状のアルキレン基であることが特に好ましい。
　式ＩＩにおけるＲ２は、解像性、引き置き時間依存抑制性及び合成容易性の観点から、単結合であることが好ましい。 Z in Formula I is a single bond, an arylene group, —C (═O) —NH— or —C (═O) —O— from the viewpoint of resolution, retention time-dependent inhibition, and ease of synthesis. It is preferably an arylene group, more preferably an —C (═O) —NH— or —C (═O) —O—, and —C (═O) —NH— or —C (═O). Particularly preferred is —O—.
Z in Formula II is preferably a single bond, an arylene group, or —C (═O) —O—, and is a single bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. Is more preferable.
R 2 in Formula I has at least one group selected from the group consisting of an ether bond, a urethane bond, and a urea bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. It is preferably a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and has at least one group selected from the group consisting of an ether bond, a urethane bond and a urea bond. It is more preferably a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms, particularly preferably a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms.
R 2 in Formula II is preferably a single bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis.
　式ＩにおけるＲ３及びＲ４はそれぞれ独立に、解像性、引き置き時間依存抑制性及び合成容易性の観点から、水素原子、又は、エーテル結合を有していてもよい炭素数１～２０の直鎖状、分岐状若しくは環状のアルキル基であることが好ましく、水素原子、又は、炭素数１～２０の直鎖状、分岐状若しくは環状のアルキル基であることがより好ましい。
　また、式Ｉにおいて、解像性及び引き置き時間依存抑制性の観点から、式ＩにおけるＲ２とＲ３とＲ４とが結合し、含窒素脂肪族環を形成している態様が好ましく、ピペリジン環を形成している態様がより好ましい。
　式ＩＩにおけるＱ１は、解像性、引き置き時間依存抑制性及び合成容易性の観点から、含窒素複素芳香族基であることが好ましく、ピリジル基、メチルピリジル基、イミダゾイル基、メチルイミダゾイル基、又は、トリアゾリル基であることがより好ましく、ピリジル基であることが更に好ましく、４－ピリジル基であることが特に好ましい。 R 3 and R 4 in formula I are each independently a hydrogen atom or a carbon number of 1 to 20 which may have an ether bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. The linear, branched or cyclic alkyl group is preferably a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
Further, in the formula I, from the viewpoints of resolution and retention time dependence suppression, an embodiment in which R 2 , R 3 and R 4 in the formula I are combined to form a nitrogen-containing aliphatic ring is preferable, An embodiment in which a piperidine ring is formed is more preferable.
Q 1 in Formula II is preferably a nitrogen-containing heteroaromatic group from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis, and is pyridyl, methylpyridyl, imidazolyl, methylimidazolyl Group or a triazolyl group is more preferable, a pyridyl group is more preferable, and a 4-pyridyl group is particularly preferable.
　ｐＫａＨが３以上の基を有する構成単位を形成するモノマーとしては、具体的には、以下のモノマーが挙げられる。
　メタクリル酸１，２，２，６，６－ペンタメチル－４－ピペリジル、メタクリル酸２－（ジメチルアミノ）エチル、アクリル酸２，２，６，６－テトラメチル－４－ピペリジル、メタクリル酸２，２，６，６－テトラメチル－４－ピペリジル、アクリル酸２，２，６，６－テトラメチル－４－ピペリジル、メタクリル酸２－（ジエチルアミノ）エチル、アクリル酸２－（ジメチルアミノ）エチル、アクリル酸２－（ジエチルアミノ）エチル、メタクリル酸Ｎ－（３－ジメチルアミノ）プロピル、アクリル酸Ｎ－（３－ジメチルアミノ）プロピル、メタクリル酸Ｎ－（３－ジエチルアミノ）プロピル、アクリル酸Ｎ－（３－ジエチルアミノ）プロピル、メタクリル酸２－（ジイソプロピルアミノ）エチル、メタクリル酸２－モルホリノエチル、アクリル酸２－モルホリノエチル、Ｎ－［３－（ジメチルアミノ）プロピル］アクリルアミド、アリルアミン、４－アミノスチレン、４－ビニルピリジン、２－ビニルピリジン、３－ビニルピリジン、１－ビニルイミダゾール、２－メチル－１－ビニルイミダゾール、１－アリルイミダゾール、１－ビニル－１，２，４－トリアゾール Specific examples of the monomer that forms a structural unit having a pKaH group of 3 or more include the following monomers.
1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2- (dimethylamino) ethyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2,2 methacrylate , 6,6-tetramethyl-4-piperidyl, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2- (diethylamino) ethyl methacrylate, 2- (dimethylamino) ethyl acrylate, acrylic acid 2- (diethylamino) ethyl, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate, N- (3-diethylamino) propyl methacrylate, N- (3-diethylamino acrylate) ) Propyl, 2- (diisopropylamino) ethyl methacrylate, 2-morpholinoethyl methacrylate, 2-morpholinoethyl crylate, N- [3- (dimethylamino) propyl] acrylamide, allylamine, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl -1-vinylimidazole, 1-allylimidazole, 1-vinyl-1,2,4-triazole
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　なお、上記モノマー中、Ｒ１２は、水素原子又はメチル基を表す。 In the above monomers, R 12 represents a hydrogen atom or a methyl group.
　また、特開２０１５－１８７６３４号公報、又は、特開２０１１－３９２６６号公報に記載されたアミノ基又は含窒素複素環基を有するモノマーも挙げられる。 In addition, monomers having an amino group or a nitrogen-containing heterocyclic group described in JP-A-2015-187634 or JP-A-2011-39266 are also included.
　上記ｐＫａＨが３以上の基を有する構成単位を少なくとも有する樹脂（例えば、酸分解性基で保護された酸基を有する構成単位、及び、ｐＫａＨが３以上の基を有する構成単位を有する重合体、又は、ｐＫａＨが３以上の基を有する構成単位を有する重合体）における上記ｐＫａＨが３以上の基を有する構成単位の含有量は、解像性及び引き置き時間依存抑制性の観点から、上記重合体の全質量に対し、０．０１質量％以上３０質量％以下であることが好ましく、０．０５質量％以上２０質量％以下であることがより好ましく、０．１質量％以上１０質量％以下であることが更に好ましく、０．４質量％以上４質量％以下であることが特に好ましく、０．５質量％以上２質量％以下であることが最も好ましい。
　また、上記重合性成分における上記ｐＫａＨが３以上の基を有する構成単位の含有量は、解像性及び引き置き時間依存抑制性の観点から、上記重合体成分の全質量に対し、０．０１質量％以上１０質量％以下であることが好ましく、０．０５質量％以上８質量％以下であることがより好ましく、０．１質量％以上５質量％以下であることが更に好ましく、０．４質量％以上４質量％以下であることが特に好ましく、０．５質量％以上２質量％以下であることが最も好ましい。 Resin having at least a structural unit having pKaH having 3 or more groups (for example, a polymer having a structural unit having an acid group protected with an acid-decomposable group, and a structural unit having pKaH having 3 or more groups, Alternatively, the content of the structural unit having pKaH having 3 or more groups in the polymer having a structural unit having pKaH having 3 or more groups is determined from the viewpoint of resolution and retention time dependence suppression. It is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.05% by mass or more and 20% by mass or less, and more preferably 0.1% by mass or more and 10% by mass or less with respect to the total mass of the coalescence. It is more preferable that it is 0.4 mass% or more and 4 mass% or less, and it is most preferable that it is 0.5 mass% or more and 2 mass% or less.
In addition, the content of the structural unit in which the pKaH has a group of 3 or more in the polymerizable component is 0.01% with respect to the total mass of the polymer component from the viewpoint of resolution and retention time-dependent suppression. It is preferably from 10% by mass to 10% by mass, more preferably from 0.05% by mass to 8% by mass, still more preferably from 0.1% by mass to 5% by mass, The content is particularly preferably from 4% by weight to 4% by weight, and most preferably from 0.5% by weight to 2% by weight.
　更に、後述するように、上記感光性樹脂層は、上記重合体におけるｐＫａＨが３以上の基以外に、ｐＫａＨが３以上の基を有する塩基性化合物等を含んでいてもよい。
　解像性及び引き置き時間依存抑制性の観点から、上記感光性樹脂層中に含まれる全てのｐＫａＨが３以上の基のうち、上記重合体成分に含まれるｐＫａＨが３以上の基の割合が、３０モル％以上であることが好ましく、５０モル％以上であることがより好ましく、８０モル％以上であることが更に好ましく、９０モル％以上１００モル％以下であることが特に好ましい。
　上記重合体ＡにおけるｐＫａＨが３以上の基を有する構成単位の含有量（含有割合：質量比）は、１３Ｃ－ＮＭＲ測定から常法により算出されるピーク強度の強度比により確認することができる。 Further, as will be described later, the photosensitive resin layer may contain a basic compound having a pKaH group of 3 or more in addition to the pKaH group of 3 or more in the polymer.
From the viewpoint of resolution and retention time-dependent suppression, among all the groups having 3 or more pKaH contained in the photosensitive resin layer, the ratio of the groups having 3 or more pKaH contained in the polymer component is 30 mol% or more, preferably 50 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more and 100 mol% or less.
The content (content ratio: mass ratio) of the structural unit having a pKaH group of 3 or more in the polymer A can be confirmed by the intensity ratio of the peak intensity calculated by 13 C-NMR measurement by a conventional method. .
－酸分解性基で保護された酸基を有する構成単位－
　上記重合体成分は、酸分解性基で保護された酸基を有する構成単位を少なくとも有する重合体を含む。
　具体的には、例えば、酸分解性基で保護された酸基を有する構成単位、及び、ｐＫａＨが３以上の基を有する構成単位を有する重合体、又は、ｐＫａＨが３以上の基を有する構成単位を有さず、かつ酸分解性基で保護された酸基を有する構成単位を有する重合体が挙げられる。
　上記重合体成分が酸分解性基で保護された酸基を有する構成単位を有する重合体を含むことにより、極めて高感度な化学増幅ポジ型の感光性樹脂層とすることができる。
　本開示における「酸分解性基で保護された酸基」は、酸基及び酸分解性基として公知のものを使用でき、特に限定されない。具体的な酸基としては、カルボキシ基、及び、フェノール性水酸基が好ましく挙げられる。また、酸分解性基で保護された酸基としては、酸により比較的分解し易い基（例えば、式Ａで表される基で保護されたエステル基、テトラヒドロピラニルエステル基、又は、テトラヒドロフラニルエステル基等のアセタール系官能基）や酸により比較的分解し難い基（例えば、ｔｅｒｔ－ブチルエステル基等の第三級アルキル基、ｔｅｒｔ－ブチルカーボネート基等の第三級アルキルカーボネート基）を用いることができる。
　これらの中でも、上記酸分解性基としては、感度及び解像性の観点から、酸がアセタールの形で保護された構造を有する基であることが好ましい。 -Constituent units having acid groups protected with acid-decomposable groups-
The polymer component includes a polymer having at least a structural unit having an acid group protected with an acid-decomposable group.
Specifically, for example, a polymer having a structural unit having an acid group protected with an acid-decomposable group and a structural unit having pKaH having 3 or more groups, or a structure having pKaH having 3 or more groups Examples thereof include a polymer having a constitutional unit having no unit and having an acid group protected with an acid-decomposable group.
When the polymer component contains a polymer having a structural unit having an acid group protected with an acid-decomposable group, a highly sensitive chemically amplified positive photosensitive resin layer can be obtained.
The “acid group protected with an acid-decomposable group” in the present disclosure may be any known acid group and acid-decomposable group, and is not particularly limited. Specific examples of the acid group preferably include a carboxy group and a phenolic hydroxyl group. The acid group protected with an acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an ester group, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester protected with a group represented by the formula A). An acetal functional group such as a group) or a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group). Can do.
Among these, the acid-decomposable group is preferably a group having a structure in which an acid is protected in the form of an acetal from the viewpoints of sensitivity and resolution.
　上記酸分解性基で保護された酸基を有する構成単位は、感度及び解像性の観点から、下記式Ａで表される構成単位であることが好ましい。 The structural unit having an acid group protected with an acid-decomposable group is preferably a structural unit represented by the following formula A from the viewpoint of sensitivity and resolution.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　式Ａ中、Ｒ３１及びＲ３２はそれぞれ独立に、水素原子、アルキル基又はアリール基を表し、少なくともＲ３１及びＲ３２のいずれか一方がアルキル基又はアリール基であり、Ｒ３３はアルキル基又はアリール基を表し、Ｒ３１又はＲ３２と、Ｒ３３とが連結して環状エーテルを形成してもよく、Ｒ３４は水素原子又はメチル基を表し、Ｘ０は単結合又は２価の連結基を表す。 In formula A, R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group or Represents an aryl group, and R 31 or R 32 and R 33 may combine to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or a divalent linking group. Represents.
　式Ａ中、Ｒ３１又はＲ３２がアルキル基の場合、炭素数１～１０のアルキル基が好ましい。Ｒ３１又はＲ３２がアリール基の場合、フェニル基が好ましい。Ｒ３１及びＲ３２は、それぞれ、水素原子又は炭素数１～４のアルキル基が好ましい。
　式Ａ中、Ｒ３３は、アルキル基又はアリール基を表し、炭素数１～１０のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましい。
　また、Ｒ３１～Ｒ３３におけるアルキル基及びアリール基は、置換基を有していてもよい。
　式Ａ中、Ｒ３１又はＲ３２と、Ｒ３３とが連結して環状エーテルを形成してもよく、Ｒ３１又はＲ３２と、Ｒ３３とが連結して環状エーテルを形成することが好ましい。環状エーテルの環員数は特に制限はないが、５又は６であることが好ましく、５であることがより好ましい。
　式Ａ中、Ｘ０は単結合又はアリーレン基を表し、単結合が好ましい。アリーレン基は、置換基を有していてもよい。
　上記式Ａで表される構成単位は、酸分解性基で保護されたカルボキシ基を有する構成単位である。上記重合体が式Ａで表される構成単位を含むことで、パターン形成時の感度に優れ、また、解像度より優れる。 In the formula A, when R 31 or R 32 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R 31 or R 32 is an aryl group, a phenyl group is preferable. R 31 and R 32 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In Formula A, R 33 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
Further, the alkyl group and aryl group in R 31 to R 33 may have a substituent.
In Formula A, R 31 or R 32 and R 33 may be linked to form a cyclic ether, and R 31 or R 32 and R 33 are preferably linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In Formula A, X 0 represents a single bond or an arylene group, and a single bond is preferable. The arylene group may have a substituent.
The structural unit represented by the formula A is a structural unit having a carboxy group protected with an acid-decomposable group. When the polymer contains the structural unit represented by the formula A, the sensitivity at the time of pattern formation is excellent and the resolution is superior.
　式Ａ中、Ｒ３４は水素原子又はメチル基を表し、上記重合体のＴｇをより低くし得るという観点から、水素原子であることが好ましい。
　より具体的には、上記重合体に含まれる式Ａで表される構成単位の全量に対し、式ＡにおけるＲ３４が水素原子である構成単位は２０質量％以上であることが好ましい。
　なお、上記酸分解性基で保護された酸基を有する構成単位中の、式ＡにおけるＲ３４が水素原子である構成単位の含有量（含有割合：質量比）は、１３Ｃ－核磁気共鳴スペクトル（ＮＭＲ）測定から常法により算出されるピーク強度の強度比により確認することができる。 In formula A, 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 can be further lowered.
More specifically, the structural unit in which R 34 in Formula A is a hydrogen atom is preferably 20% by mass or more based on the total amount of the structural unit represented by Formula A contained in the polymer.
The content (content ratio: mass ratio) of the structural unit in which R 34 in Formula A is a hydrogen atom in the structural unit having an acid group protected with an acid-decomposable group is 13 C-nuclear magnetic resonance. It can be confirmed by the intensity ratio of the peak intensity calculated from the spectrum (NMR) measurement by a conventional method.
　式Ａで表される構成単位の中でも、下記式Ａ２で表される構成単位が、パターン形成時の感度を更に高める観点からより好ましい。 Among the structural units represented by the formula A, the structural unit represented by the following formula A2 is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　式Ａ２中、Ｒ３４は水素原子又はメチル基を表し、Ｒ３５～Ｒ４１はそれぞれ独立に、水素原子又は炭素数１～４のアルキル基を表す。
　式Ａ２中、Ｒ３４は水素原子が好ましい。
　式Ａ２中、Ｒ３５～Ｒ４１は、水素原子が好ましい。 In formula A2, R 34 represents a hydrogen atom or a methyl group, and R 35 to R 41 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In formula A2, R 34 is preferably a hydrogen atom.
In formula A2, R 35 to R 41 are preferably hydrogen atoms.
　式Ａで表される、酸分解性基で保護されたカルボキシ基を有する構成単位の好ましい具体例としては、下記の構成単位が例示できる。なお、Ｒ３４は水素原子又はメチル基を表す。 Preferable specific examples of the structural unit represented by formula A having a carboxy group protected with an acid-decomposable group include the following structural units. R 34 represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　また、上記酸分解性基で保護された酸基を有する構成単位としては、パターン形状の変形抑制の観点から、下記式Ａ３で表される構成単位が好ましい。 The structural unit having an acid group protected with an acid-decomposable group is preferably a structural unit represented by the following formula A3 from the viewpoint of suppressing deformation of the pattern shape.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　式Ａ３中、ＲＢ１及びＲＢ２はそれぞれ独立に、水素原子、アルキル基又はアリール基を表し、少なくともＲＢ１及びＲＢ２のいずれか一方がアルキル基又はアリール基であり、ＲＢ３はアルキル基又はアリール基を表し、ＲＢ１又はＲＢ２と、ＲＢ３とが連結して環状エーテルを形成してもよく、ＲＢ４は水素原子又はメチル基を表し、ＸＢは単結合又は二価の連結基を表し、ＲＢ１２は置換基を表し、ｎは０～４の整数を表す。 In Formula A3, R B1 and R B2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R B1 and R B2 is an alkyl group or an aryl group, and R B3 is an alkyl group or Represents an aryl group, R B1 or R B2 and R B3 may be linked to form a cyclic ether, R B4 represents a hydrogen atom or a methyl group, and X B represents a single bond or a divalent linking group; R B12 represents a substituent, and n represents an integer of 0 to 4.
　式Ａ３中、ＲＢ１又はＲＢ２がアルキル基の場合、炭素数は１～１０のアルキル基が好ましい。ＲＢ１又はＲＢ２がアリール基の場合、フェニル基が好ましい。ＲＢ１及びＲＢ２はそれぞれ独立に、水素原子又は炭素数１～４のアルキル基が好ましい。
　式Ａ３中、ＲＢ３は、アルキル基又はアリール基を表し、炭素数１～１０のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましい。
　また、ＲＢ１～ＲＢ３におけるアルキル基及びアリール基は、置換基を有していてもよい。
　式Ａ３中、ＲＢ１又はＲＢ２と、ＲＢ３とが連結して環状エーテルを形成してもよく、ＲＢ１又はＲＢ２と、ＲＢ３とが連結して環状エーテルを形成することが好ましい。環状エーテルの環員数は特に制限はないが、５又は６であることが好ましく、５であることがより好ましい。
　式Ａ３中、ＸＢは単結合又は二価の連結基を表し、単結合又はアルキレン基、－Ｃ（＝Ｏ）Ｏ－、－Ｃ（＝Ｏ）ＮＲＮ－、－Ｏ－又はこれらの組み合わせが好ましく、単結合がより好ましい。アルキレン基は、直鎖状でも分岐を有していても環状構造を有していてもよく、置換基を有していてもよい。アルキレン基の炭素数は１～１０が好ましく、１～４がより好ましい。ＸＢが－Ｃ（＝Ｏ）Ｏ－を含む場合、－Ｃ（＝Ｏ）Ｏ－に含まれる炭素原子と、ＲＢ４が結合した炭素原子とが直接結合する態様が好ましい。ＸＢが－Ｃ（＝Ｏ）ＮＲＮ－を含む場合、－Ｃ（＝Ｏ）ＮＲＮ－に含まれる炭素原子と、ＲＢ４が結合した炭素原子とが直接結合する態様が好ましい。ＲＮはアルキル基又は水素原子を表し、炭素数１～４のアルキル基又は水素原子が好ましく、水素原子がより好ましい。
　式Ａ３中、ＲＢ１～ＲＢ３を含む基と、ＸＢとは、互いにパラ位で結合することが好ましい。
　式Ａ３中、ＲＢ１２は置換基を表し、アルキル基又はハロゲン原子が好ましい。アルキル基の炭素数は、１～１０が好ましく、１～４がより好ましい。
　式Ａ３中、ｎは０～４の整数を表し、０又は１が好ましく、０がより好ましい。 In Formula A3, when R B1 or R B2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R B1 or R B2 is an aryl group, a phenyl group is preferable. R B1 and R B2 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In Formula A3, R B3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
In addition, the alkyl group and aryl group in R B1 to R B3 may have a substituent.
In Formula A3, R B1 or R B2 and R B3 may be linked to form a cyclic ether, and R B1 or R B2 and R B3 are preferably linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In Formula A3, X B represents a single bond or a divalent linking group, and represents a single bond or an alkylene group, —C (═O) O—, —C (═O) NR N —, —O—, or a combination thereof. Are preferable, and a single bond is more preferable. The alkylene group may be linear, branched or cyclic, and may have a substituent. The alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. When X B contains —C (═O) O—, an embodiment in which the carbon atom contained in —C (═O) O— and the carbon atom bonded to R B4 are directly bonded is preferable. When containing, -C (= O) NR N - - is X B -C (= O) NR N and carbon atoms contained in a mode in which the carbon atom to which R B4 is bonded is directly bonded is preferable. R N represents an alkyl group or a hydrogen atom, preferably an alkyl group or a hydrogen atom having 1 to 4 carbon atoms, more preferably a hydrogen atom.
In formula A3, the group containing R B1 to R B3 and X B are preferably bonded to each other at the para position.
In Formula A3, R B12 represents a substituent, and is preferably an alkyl group or a halogen atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
In the formula A3, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
　式Ａ３中、ＲＢ４は水素原子又はメチル基を表し、重合体のＴｇをより低くし得るという観点から、水素原子であることが好ましい。
　より具体的には、重合体に含まれる上記酸分解性基で保護された酸基を有する構成単位の全含有量に対し、式Ａ３におけるＲＢ４が水素原子である構成単位は２０質量％以上であることが好ましい。
　なお、上記酸分解性基で保護された酸基を有する構成単位中の、式Ａ３におけるＲＢ４が水素原子である構成単位の含有量（含有割合：質量比）は、１３Ｃ－核磁気共鳴スペクトル（ＮＭＲ）測定から常法により算出されるピーク強度の強度比により確認することができる。 In Formula A3, R B4 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of lowering the Tg of the polymer.
More specifically, with respect to the total content of the structural unit having an acid group protected by the acid-decomposable group contained in the polymer, the structural unit in which R B4 in formula A3 is a hydrogen atom is 20% by mass or more. It is preferable that
In the structural unit having an acid group protected with an acid-decomposable group, the content (content ratio: mass ratio) of the structural unit in which R B4 in formula A3 is a hydrogen atom is 13 C-nuclear magnetic resonance. It can be confirmed by the intensity ratio of the peak intensity calculated from the spectrum (NMR) measurement by a conventional method.
　式Ａ３で表される構成単位の中でも、パターン形状の変形抑制の観点から、下記式Ａ４で表される構成単位がより好ましい。 Among the structural units represented by the formula A3, the structural unit represented by the following formula A4 is more preferable from the viewpoint of suppressing deformation of the pattern shape.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　式Ａ４中、ＲＢ４は水素原子又はメチル基を表し、ＲＢ５～ＲＢ１１はそれぞれ独立に、水素原子又は炭素数１～４のアルキル基を表し、ＲＢ１２は置換基を表し、ｎは０～４の整数を表す。
　式Ａ４中、ＲＢ４は水素原子が好ましい。
　式Ａ４中、ＲＢ５～ＲＢ１１は、水素原子が好ましい。
　式Ａ４中、ＲＢ１２は置換基を表し、アルキル基又はハロゲン原子が好ましい。アルキル基の炭素数は、１～１０が好ましく、１～４がより好ましい。
　式Ａ４中、ｎは０～４の整数を表し、０又は１が好ましく、０がより好ましい。 In Formula A4, R B4 represents a hydrogen atom or a methyl group, R B5 to R B11 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R B12 represents a substituent, and n is 0 Represents an integer of ~ 4.
In formula A4, R B4 is preferably a hydrogen atom.
In formula A4, R B5 to R B11 are preferably hydrogen atoms.
In Formula A4, R B12 represents a substituent, and is preferably an alkyl group or a halogen atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
In the formula A4, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
　式Ａ４で表される構成単位Ａ４の好ましい具体例としては、下記の構成単位が例示できる。なお、ＲＢ４は水素原子又はメチル基を表す。 Preferable specific examples of the structural unit A4 represented by the formula A4 include the following structural units. R B4 represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　重合体に含まれる上記酸分解性基で保護された酸基を有する構成単位は、１種であっても、２種以上であってもよい。
　重合体における上記酸分解性基で保護された酸基を有する構成単位の含有量は、重合体の全質量に対して、１０質量％以上であることが好ましく、１０質量％～９０質量％であることがより好ましく、２０質量％～７０質量％であることが更に好ましい。
　重合体における上記酸分解性基で保護された酸基を有する構成単位の含有量（含有割合：質量比）は、１３Ｃ－ＮＭＲ測定から常法により算出されるピーク強度の強度比により確認することができる。
　また、全ての重合体成分を構成単位（モノマー単位）に分解したうえで、上記重合体成分における上記酸分解性基で保護された酸基を有する構成単位の含有割合は、重合体成分の全質量に対して、５質量％～８０質量％であることが好ましく、１０質量％～８０質量％であることがより好ましく、２０質量％～７０質量％であることが特に好ましい。 The structural unit having an acid group protected by the acid-decomposable group contained in the polymer may be one type or two or more types.
The content of the structural unit having an acid group protected by the acid-decomposable group in the polymer is preferably 10% by mass or more with respect to the total mass of the polymer, and is 10% by mass to 90% by mass. More preferred is 20% by mass to 70% by mass.
The content (content ratio: mass ratio) of the structural unit having an acid group protected by the acid-decomposable group in the polymer is confirmed by the intensity ratio of the peak intensity calculated by 13 C-NMR measurement by a conventional method. be able to.
Moreover, after decomposing all the polymer components into structural units (monomer units), the content ratio of the structural unit having an acid group protected by the acid-decomposable group in the polymer component is the total content of the polymer components. The mass is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 80% by mass, and particularly preferably 20% by mass to 70% by mass.
　上記重合体成分における酸分解性基で保護された酸基を有する構成単位の含有質量割合ＭＡとｐＫａＨが３以上の基を有する構成単位の含有質量割合ＭＢとの質量比（ＭＡ／ＭＢ）は、解像性及び引き置き時間依存抑制性の観点から、５～２００であることが好ましく、１０～１５０であることがより好ましく、２０～１００であることが更に好ましい。 The mass ratio of the content mass ratio M B of structural units containing a mass ratio M A and pKaH constituent units having protected acid groups in the acid-decomposable group in the polymer component having three or more groups (M A / M B ) is preferably from 5 to 200, more preferably from 10 to 150, and even more preferably from 20 to 100, from the viewpoints of resolution and retention time-dependent suppression.
　上記重合体成分における重合体は、現像性及び解像性の観点から、酸分解性基で保護された酸基を有する構成単位及びｐＫａＨが３以上の基を有する構成単位以外の構成単位（例えば、後述する酸基を有する構成単位、及び、その他の構成単位）を更に有することが好ましい。 From the viewpoint of developability and resolution, the polymer in the polymer component is a structural unit other than a structural unit having an acid group protected with an acid-decomposable group and a structural unit having a pKaH of 3 or more (for example, It is preferable to further include a structural unit having an acid group described below and other structural units).
－酸基を有する構成単位－
　上記重合体成分における重合体はそれぞれ独立に、現像性及び解像性の観点から、酸基を有する構成単位を含んでいてもよい。
　酸基を有する構成単位は、保護基、例えば、酸分解性基で保護されていない酸基、すなわち、保護基を有さない酸基を有する構成単位である。重合体成分が酸基を有する構成単位を有する重合体を含むことで、パターン形成時の感度が良好となり、パターン露光後の現像工程においてアルカリ性の現像液に溶けやすくなり、現像時間の短縮化を図ることができる。
　本明細書における酸基とは、ｐＫａが１２以下のプロトン解離性基を意味する。酸基は、通常、酸基を形成しうるモノマーを用いて、酸基を有する構成単位として、重合体に組み込まれる。感度向上の観点から、酸基のｐＫａは、１０以下が好ましく、６以下がより好ましい。また、酸基のｐＫａは、－５以上であることが好ましい。 -Structural unit having an acid group-
The polymers in the polymer component may each independently contain a structural unit having an acid group from the viewpoints of developability and resolution.
The structural unit having an acid group is a structural unit having a protective group, for example, an acid group not protected by an acid-decomposable group, that is, an acid group having no protective group. By including a polymer having a structural unit having an acid group in the polymer component, the sensitivity at the time of pattern formation becomes good, and it becomes easier to dissolve in an alkaline developer in the development process after pattern exposure, thereby shortening the development time. Can be planned.
The acid group in this specification means a proton dissociable group having a pKa of 12 or less. The acid group is usually incorporated into the polymer as a structural unit having an acid group using a monomer capable of forming an acid group. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. The pKa of the acid group is preferably −5 or more.
　酸分解性基で保護されていない酸基を有する構成単位を重合体成分中の重合体のいずれかに少なくとも有し、重合体成分のガラス転移温度を９０℃以下とすることで、重合体を含有するポジ型感光性樹脂層は、転写性、仮支持体からの剥離性を良好なレベルに維持しつつ、パターン形成時の解像度及び感度がより良好となる。 Having at least a constituent unit having an acid group not protected by an acid-decomposable group in any of the polymers in the polymer component, and setting the glass transition temperature of the polymer component to 90 ° C. or less, The positive type photosensitive resin layer to be contained has better resolution and sensitivity at the time of pattern formation while maintaining transferability and peelability from the temporary support at good levels.
　上記酸基としては、カルボキシ基、スルホンアミド基、ホスホン酸基、スルホン酸基、フェノール性水酸基、及び、スルホニルイミド基等が例示される。中でも、カルボキシ基及びフェノール性水酸基よりなる群から選ばれる少なくとも１種の酸基が好ましい。
　重合体への酸基を有する構成単位の導入は、酸基を有するモノマーを共重合させることで行うことができる。
　酸基を有する構成単位は、スチレンに由来する構成単位若しくはビニル化合物に由来する構成単位に対して酸基が置換した構成単位、又は、（メタ）アクリル酸に由来する構成単位であることがより好ましい。 Examples of the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonylimide group. Among these, at least one acid group selected from the group consisting of a carboxy group and a phenolic hydroxyl group is preferable.
Introduction of a structural unit having an acid group into the polymer can be carried out by copolymerizing a monomer having an acid group.
The structural unit having an acid group is more preferably a structural unit derived from styrene or a structural unit derived from a vinyl compound, or a structural unit derived from (meth) acrylic acid. preferable.
　酸基を有する構成単位としては、カルボキシ基を有する構成単位、又は、フェノール性水酸基を有する構成単位が、パターン形成時の感度がより良好となるという観点から好ましい。
　酸基を有する構成単位を形成しうる酸基を有するモノマーは既述の例に限定されない。 As the structural unit having an acid group, a structural unit having a carboxy group or a structural unit having a phenolic hydroxyl group is preferable from the viewpoint that sensitivity at the time of pattern formation becomes better.
The monomer having an acid group that can form a structural unit having an acid group is not limited to the examples described above.
　重合体に含まれる酸基を有する構成単位は、１種のみであっても、２種以上であってもよい。
　上記重合体が、酸基を有する構成単位を有する場合、酸基を有する構成単位を有する重合体は、重合体の全質量に対し、酸基を有する構成単位を０．１質量％～２０質量％含むことが好ましく、０．５質量％～１５質量％含むことがより好ましく、１質量％～１０質量％含むことが更に好ましい。上記範囲であると、パターン形成性がより良好となる。
　重合体における酸基を有する構成単位の含有量（含有割合：質量比）は、１３Ｃ－ＮＭＲ測定から常法により算出されるピーク強度の強度比により確認することができる。
　また、全ての重合体成分を構成単位（モノマー単位）に分解したうえで、上記重合体成分における上記酸基を有する構成単位の含有割合は、重合体成分の全質量に対して、０．１質量％～２０質量％であることが好ましく、０．５質量％～１５質量％であることがより好ましく、１質量％～１０質量％であることが特に好ましい。 The structural unit having an acid group contained in the polymer may be only one type or two or more types.
When the polymer has a structural unit having an acid group, the polymer having a structural unit having an acid group has a structural unit having an acid group in an amount of 0.1% by mass to 20% by mass with respect to the total mass of the polymer. %, Preferably 0.5% to 15% by weight, more preferably 1% to 10% by weight. When it is in the above range, the pattern formability becomes better.
The content (content ratio: mass ratio) of the structural unit having an acid group in the polymer can be confirmed by the intensity ratio of peak intensity calculated by 13 C-NMR measurement by a conventional method.
Moreover, after decomposing | disassembling all the polymer components into a structural unit (monomer unit), the content rate of the structural unit which has the said acid group in the said polymer component is 0.1 with respect to the total mass of a polymer component. The mass is preferably 20% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and particularly preferably 1% by mass to 10% by mass.
－その他の構成単位－
　重合体は、既述の、酸分解性基で保護された酸基を有する構成単位、ｐＫａＨが３以上の基を有する構成単位、及び、酸基を有する構成単位以外の、その他の構成単位を、本開示に係る感光性転写材料の効果を損なわない範囲で含んでいてもよい。
　その他の構成単位を形成するモノマーとしては、特に制限はなく、例えば、スチレン類、（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸環状アルキルエステル、（メタ）アクリル酸アリールエステル、不飽和ジカルボン酸ジエステル、ビシクロ不飽和化合物、マレイミド化合物、不飽和芳香族化合物、共役ジエン系化合物、不飽和モノカルボン酸、不飽和ジカルボン酸、不飽和ジカルボン酸無水物、脂肪族環式骨格を有する基、その他の不飽和化合物を挙げることができる。
　その他の構成単位を用いて、種類及び含有量の少なくともいずれかを調整することで、重合体の諸特性を調整することができる。特に、その他の構成単位を適切に使用することで、重合体成分のＴｇを９０℃以下に容易に調整することができる。
　重合体は、その他の構成単位を１種のみ含んでもよく、２種以上含んでいてもよい。 -Other structural units-
The polymer includes other structural units other than the structural unit having an acid group protected with an acid-decomposable group, the structural unit having a pKaH of 3 or more, and the structural unit having an acid group. The photosensitive transfer material according to the present disclosure may be included within a range that does not impair the effect.
There is no restriction | limiting in particular as a monomer which forms other structural units, For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid Diester, bicyclounsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride, group having aliphatic cyclic skeleton, other Mention may be made of unsaturated compounds.
Various characteristics of the polymer can be adjusted by adjusting at least one of the type and content using other structural units. In particular, the Tg of the polymer component can be easily adjusted to 90 ° C. or lower by appropriately using other structural units.
The polymer may contain only 1 type of other structural units, and may contain 2 or more types.
　その他の構成単位は、具体的には、スチレン、ｔｅｒｔ－ブトキシスチレン、メチルスチレン、α－メチルスチレン、アセトキシスチレン、メトキシスチレン、エトキシスチレン、クロロスチレン、ビニル安息香酸メチル、ビニル安息香酸エチル、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸イソボルニル、アクリロニトリル、又は、エチレングリコールモノアセトアセテートモノ（メタ）アクリレートなどを重合して形成される構成単位を挙げることができる。その他、特開２００４－２６４６２３号公報の段落００２１～段落００２４に記載の化合物を挙げることができる。 Other structural units are specifically styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, (meta ) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth And a structural unit formed by polymerizing benzyl acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate, or the like. In addition, the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be given.
　また、その他の構成単位としては、芳香環を有する構成単位、又は、脂肪族環式骨格を有する構成単位が、得られる転写材料の電気特性を向上させる観点で好ましい。これら構成単位を形成するモノマーとして、具体的には、スチレン、ｔｅｒｔ－ブトキシスチレン、メチルスチレン、α－メチルスチレン、ジシクロペンタニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、及び、ベンジル（メタ）アクリレート等が挙げられる。中でも、シクロヘキシル（メタ）アクリレート由来の構成単位が好ましく挙げられる。 As other structural units, structural units having an aromatic ring or structural units having an aliphatic cyclic skeleton are preferable from the viewpoint of improving the electrical properties of the obtained transfer material. Specific examples of monomers that form these structural units include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, And benzyl (meth) acrylate etc. are mentioned. Especially, the structural unit derived from a cyclohexyl (meth) acrylate is mentioned preferably.
　また、その他の構成単位を形成するモノマーとしては、例えば、（メタ）アクリル酸アルキルエステルが、密着性の観点で好ましい。中でも、炭素数４～１２のアルキル基を有する（メタ）アクリル酸アルキルエステルが密着性の観点でより好ましい。具体的には、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ｎ－ブチル、及び、（メタ）アクリル酸２－エチルヘキシルが挙げられる。 In addition, as a monomer that forms other structural unit, for example, (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Among them, (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
　その他の構成単位の含有量は、重合体の全質量に対し、７０質量％以下が好ましく、６０質量％以下がより好ましく、５０質量％以下が更に好ましい。下限値としては、０質量％でもよいが、１質量％以上であることが好ましく、５質量％以上であることがより好ましい。上記範囲であると、解像度及び密着性がより向上する。 The content of other structural units is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less with respect to the total mass of the polymer. The lower limit may be 0% by mass, but is preferably 1% by mass or more, and more preferably 5% by mass or more. Within the above range, the resolution and adhesion are further improved.
　中でも、上記重合体成分に含まれる重合体はそれぞれ独立に、ラミネート適性及び解像性の観点から、カルボン酸エステル構造を有する構成単位を含むことが好ましい。カルボン酸エステル構造を有する構成単位としては、ラミネート適性及び解像性の観点から、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２－エチルヘキシル又は（メタ）アクリル酸ベンジル由来の構成単位が好ましく、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸シクロヘキシル又は（メタ）アクリル酸ベンジル由来の構成単位がより好ましい。
　更に、上記ａ１又はａ２に示す重合体は、ラミネート適性及び解像性の観点から、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸シクロヘキシル又は（メタ）アクリル酸ベンジル由来の構成単位を有することが好ましく、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸シクロヘキシル又は（メタ）アクリル酸ベンジル由来の構成単位を２種以上有することがより好ましい。 Especially, it is preferable that the polymer contained in the said polymer component contains the structural unit which has a carboxylic ester structure from a laminated suitability and a resolution viewpoint each independently. As the structural unit having a carboxylic acid ester structure, from the viewpoints of laminate suitability and resolution, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate Preferred are structural units derived from 2-ethylhexyl (meth) acrylate or benzyl (meth) acrylate, such as methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate or benzyl (meth) acrylate. The structural unit derived from is more preferable.
Furthermore, the polymer shown in the above a1 or a2 is derived from methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate or benzyl (meth) acrylate from the viewpoint of laminating suitability and resolution. It is preferable to have 2 or more types of structural units derived from methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate or benzyl (meth) acrylate.
　また、上記重合体成分に含まれる重合体はそれぞれ独立に、ラミネート適性及び解像性の観点から、上記カルボン酸エステル構造を有する構成単位として、下記式Ｃで表される構成単位を含むことが好ましい。 In addition, each of the polymers contained in the polymer component independently contains a structural unit represented by the following formula C as a structural unit having the carboxylic acid ester structure from the viewpoint of laminating suitability and resolution. preferable.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　式Ｃ中、ＲＣ１は、水素原子又はメチル基を表し、ＲＣ２は、炭素数１～２０の直鎖状、分岐状若しくは環状のアルキル基、又は、炭素数７～２０のアラルキル基を表す。 In Formula C, R C1 represents a hydrogen atom or a methyl group, and R C2 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. .
　式ＣにおけるＲＣ２は、ラミネート適性及び解像性の観点から、炭素数１～１０の直鎖状、分岐状若しくは環状のアルキル基、又は、炭素数７～１６のアラルキル基であることが好ましく、炭素数１～６の直鎖状、分岐状若しくは環状のアルキル基、又は、ベンジル基であることがより好ましく、メチル基、エチル基、シクロヘキシル基、又は、ベンジル基であることが特に好ましい。 R C2 in Formula C is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 16 carbon atoms from the viewpoint of laminating suitability and resolution. And more preferably a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a benzyl group, and particularly preferably a methyl group, an ethyl group, a cyclohexyl group, or a benzyl group.
　また、上記ａ１又はａ２に示す重合体は、ラミネート適性及び解像性の観点から、カルボン酸エステル構造を有する構成単位を、重合体の全質量に対し、３０質量％以上含むことが好ましく、５０質量％以上含むことがより好ましく、５０質量％～８０質量％含むことが更に好ましく、６０質量％～７５質量％含むことが特に好ましい。
　また、全ての重合体成分を構成単位（モノマー単位）に分解したうえで、上記重合体成分における上記カルボン酸エステル構造を有する構成単位の含有割合は、重合体成分の全質量に対して、３０質量％以上であることが好ましく、５０質量％以上であることがより好ましく、５０質量％～８０質量％であることが特に好ましい。 In addition, the polymer shown in a1 or a2 preferably contains 30% by mass or more of a structural unit having a carboxylic acid ester structure with respect to the total mass of the polymer, from the viewpoint of laminating suitability and resolution. More preferably, the content is more preferably 50% by mass to 80% by mass, and particularly preferably 60% by mass to 75% by mass.
Moreover, after decomposing | disassembling all the polymer components into a structural unit (monomer unit), the content rate of the structural unit which has the said carboxylic acid ester structure in the said polymer component is 30 with respect to the total mass of a polymer component. It is preferably at least mass%, more preferably at least 50 mass%, particularly preferably from 50 mass% to 80 mass%.
－重合体の製造方法－
　重合体の製造方法（合成法）は特に限定されないが、一例を挙げると、酸分解性基で保護された酸基を有する構成単位を形成するための重合性単量体、ｐＫａＨが３以上の基を有する構成単位を形成するための重合性単量体、更に必要に応じて、式Ｃで表される構成単位を形成するための重合性単量体を含む有機溶剤中、重合開始剤を用いて重合することにより合成することができる。また、いわゆる高分子反応により他の重合体から合成することもできる。 -Polymer production method-
The polymer production method (synthesis method) is not particularly limited. For example, a polymerizable monomer for forming a structural unit having an acid group protected by an acid-decomposable group, pKaH is 3 or more. A polymerization initiator for forming a structural unit having a group, and, if necessary, a polymerization initiator in an organic solvent containing a polymerizable monomer for forming a structural unit represented by formula C. It can synthesize | combine by superposing | polymerizing using. It can also be synthesized from other polymers by so-called polymer reaction.
　本開示における上記感光性樹脂層は、良好な密着性を発現させる観点から、感光性樹脂層の全質量に対し、上記重合体成分を５０質量％～９９．９質量％の割合で含むことが好ましく、７０質量％～９８質量％の割合で含むことがより好ましい。 The photosensitive resin layer in the present disclosure may contain the polymer component in a proportion of 50% by mass to 99.9% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of developing good adhesion. Preferably, it is contained in a proportion of 70% by mass to 98% by mass.
－他の重合体－
　上記感光性樹脂層は、重合体成分として、上記ａ１又はａ２に示す重合体に加え、本開示に係る感光性転写材料の効果を損なわない範囲において、酸分解性基で保護された酸基を有する構成単位及びｐＫａＨが３以上の基を有する構成単位を含まない重合体（「他の重合体」と称する場合がある。）を更に含んでいてもよい。上記感光性樹脂層が他の重合体を含む場合、他の重合体の配合量は、全重合体成分中、５０質量％以下であることが好ましく、３０質量％以下であることがより好ましく、２０質量％以下であることが更に好ましい。 -Other polymers-
The photosensitive resin layer has, as a polymer component, 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 in addition to the polymer shown in a1 or a2. It may further contain a polymer having no structural unit and a structural unit having pKaH having a group of 3 or more (sometimes referred to as "other polymer"). When the photosensitive resin layer contains another polymer, the blending amount of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less in the total polymer component, More preferably, it is 20 mass% or less.
　上記感光性樹脂層は、上記ａ１又はａ２に示す重合体に加え、他の重合体を１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。
　他の重合体として、例えばポリヒドロキシスチレンを用いることができ、市販されている、ＳＭＡ　１０００Ｐ、ＳＭＡ　２０００Ｐ、ＳＭＡ　３０００Ｐ、ＳＭＡ　１４４０Ｆ、ＳＭＡ　１７３５２Ｐ、ＳＭＡ　２６２５Ｐ、及び、ＳＭＡ　３８４０Ｆ（以上、サートマー社製）、ＡＲＵＦＯＮ　ＵＣ－３０００、ＡＲＵＦＯＮ　ＵＣ－３５１０、ＡＲＵＦＯＮ　ＵＣ－３９００、ＡＲＵＦＯＮ　ＵＣ－３９１０、ＡＲＵＦＯＮ　ＵＣ－３９２０、及び、ＡＲＵＦＯＮ　ＵＣ－３０８０（以上、東亞合成（株）製）、並びに、Ｊｏｎｃｒｙｌ　６９０、Ｊｏｎｃｒｙｌ　６７８、Ｊｏｎｃｒｙｌ　６７、及び、Ｊｏｎｃｒｙｌ　５８６（以上、ＢＡＳＦ社製）等を用いることもできる。 In addition to the polymer shown to said a1 or a2, the said photosensitive resin layer may contain only 1 type of other polymers, and may contain 2 or more types.
As other polymers, for example, polyhydroxystyrene can be used and are commercially available, such as SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer). , ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), and Joncryl 690, Joncryl 6 Joncryl 67, Joncryl 586 (manufactured by BASF) or the like can also be used.
＜＜光酸発生剤＞＞
　上記感光性樹脂層は、光酸発生剤を含有する。
　本開示で使用される光酸発生剤としては、紫外線、遠紫外線、Ｘ線、及び、荷電粒子線等の活性光線を照射することにより酸を発生することができる化合物である。
　本開示で使用される光酸発生剤としては、波長３００ｎｍ以上、好ましくは波長３００ｎｍ～４５０ｎｍの活性光線に感応し、酸を発生する化合物が好ましいが、その化学構造は制限されない。また、波長３００ｎｍ以上の活性光線に直接感応しない光酸発生剤についても、増感剤と併用することによって波長３００ｎｍ以上の活性光線に感応し、酸を発生する化合物であれば、増感剤と組み合わせて好ましく用いることができる。
　本開示で使用される光酸発生剤としては、ｐＫａが４以下の酸を発生する光酸発生剤が好ましく、ｐＫａが３以下の酸を発生する光酸発生剤がより好ましく、ｐＫａが２以下の酸を発生する光酸発生剤が特に好ましい。ｐＫａの下限値は特に定めないが、例えば、－１０．０以上であることが好ましい。 << Photoacid generator >>
The photosensitive resin layer contains a photoacid generator.
The photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiation with actinic rays such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
The photoacid generator used in the present disclosure is preferably a compound that generates an acid in response to an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but its chemical structure is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can be used as a sensitizer as long as it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
The photoacid generator used in the present disclosure is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a pKa of 2 or less. A photoacid generator that generates an acid is particularly preferable. The lower limit value of pKa is not particularly defined, but is preferably −10.0 or more, for example.
　光酸発生剤としては、イオン性光酸発生剤と、非イオン性光酸発生剤とを挙げることができる。
　また、光酸発生剤としては、感度及び解像度の観点から、後述するオニウム塩化合物、及び、後述するオキシムスルホネート化合物よりなる群から選ばれた少なくとも１種の化合物を含むことが好ましく、オキシムスルホネート化合物を含むことがより好ましい。 Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.
The photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound described later from the viewpoint of sensitivity and resolution, and an oxime sulfonate compound. It is more preferable to contain.
　非イオン性光酸発生剤の例として、トリクロロメチル－ｓ－トリアジン類、ジアゾメタン化合物、イミドスルホネート化合物、及び、オキシムスルホネート化合物などを挙げることができる。これらの中でも、感度、解像度、及び、密着性の観点から、光酸発生剤がオキシムスルホネート化合物であることが好ましい。これら光酸発生剤は、１種単独又は２種類以上を組み合わせて使用することができる。トリクロロメチル－ｓ－トリアジン類、及び、ジアゾメタン誘導体の具体例としては、特開２０１１－２２１４９４号公報の段落００８３～段落００８８に記載の化合物が例示できる。 Examples of nonionic photoacid generators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, the photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP 2011-212494A.
　オキシムスルホネート化合物、すなわち、オキシムスルホネート構造を有する化合物としては、下記式（Ｂ１）で表されるオキシムスルホネート構造を有する化合物が好ましい。 As the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure, a compound having an oxime sulfonate structure represented by the following formula (B1) is preferable.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　式（Ｂ１）中、Ｒ２１は、アルキル基又はアリール基を表し、＊は他の原子又は他の基との結合部位を表す。 In formula (B1), R 21 represents an alkyl group or an aryl group, and * represents a bonding site with another atom or another group.
　式（Ｂ１）で表されるオキシムスルホネート構造を有する化合物は、いずれの基も置換されてもよく、Ｒ２１におけるアルキル基は、直鎖状であっても、分岐構造を有していても、環構造を有していてもよい。許容される置換基は以下に説明する。
　Ｒ２１のアルキル基としては、炭素数１～１０の、直鎖状又は分岐状アルキル基が好ましい。Ｒ２１のアルキル基は、炭素数６～１１のアリール基、炭素数１～１０のアルコキシ基、シクロアルキル基（７，７－ジメチル－２－オキソノルボルニル基などの有橋式脂環基を含む、好ましくはビシクロアルキル基等）、又は、ハロゲン原子で置換されてもよい。
　Ｒ２１のアリール基としては、炭素数６～１８のアリール基が好ましく、フェニル基又はナフチル基がより好ましい。Ｒ２１のアリール基は、炭素数１～４のアルキル基、アルコキシ基及びハロゲン原子よりなる群から選ばれた１つ以上の基で置換されてもよい。 In the compound having an oxime sulfonate structure represented by the formula (B1), any group may be substituted, and the alkyl group in R 21 may be linear or branched. It may have a ring structure. Acceptable substituents are described below.
The alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R 21 is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or other bridged alicyclic group) , Preferably a bicycloalkyl group or the like), or a halogen atom.
The aryl group for R 21 is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R 21 may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a halogen atom.
　式（Ｂ１）で表されるオキシムスルホネート構造を有する化合物は、特開２０１４－８５６４３号公報の段落００７８～０１１１に記載のオキシムスルホネート化合物であることも好ましい。 The compound having an oxime sulfonate structure represented by the formula (B1) is preferably an oxime sulfonate compound described in paragraphs 0078 to 0111 of JP-A-2014-85643.
　イオン性光酸発生剤の例として、ジアリールヨードニウム塩類及びトリアリールスルホニウム塩類等のオニウム塩化合物、第四級アンモニウム塩類等を挙げることができる。これらのうち、オニウム塩化合物が好ましく、トリアリールスルホニウム塩類及びジアリールヨードニウム塩類が特に好ましい。 Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, quaternary ammonium salts, and the like. Of these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.
　イオン性光酸発生剤としては特開２０１４－８５６４３号公報の段落０１１４～０１３３に記載のイオン性光酸発生剤も好ましく用いることができる。 As the ionic photoacid generator, ionic photoacid generators described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.
　光酸発生剤は、１種単独で使用してもよいし、２種以上を併用してもよい。
　上記感光性樹脂層における光酸発生剤の含有量は、感度、解像度の観点から、上記感光性樹脂層の全質量に対して、０．１質量％～１０質量％であることが好ましく、０．５質量％～５質量％であることがより好ましい。 A photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
The content of the photoacid generator in the photosensitive resin layer is preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of sensitivity and resolution. More preferably, the content is 5% by mass to 5% by mass.
＜＜塩基性化合物＞＞
　上記感光性樹脂層は、塩基性化合物を更に含んでいてもよい。
　本開示における塩基性化合物の分子量は、２，０００未満であり、１，０００未満であることが好ましい。
　塩基性化合物としては、化学増幅ポジ型レジストで用いられる塩基性化合物の中から任意に選択して使用することができる。例えば、脂肪族アミン、芳香族アミン、複素環式アミン、第四級アンモニウムヒドロキシド、及び、カルボン酸の第四級アンモニウム塩等が挙げられる。これらの具体例としては、特開２０１１－２２１４９４号公報の段落０２０４～段落０２０７に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。 << basic compound >>
The photosensitive resin layer may further contain a basic compound.
The molecular weight of the basic compound in the present disclosure is less than 2,000, and preferably less than 1,000.
As the basic compound, any basic compound used in a chemically amplified positive resist can be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include compounds described in JP-A-2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
　具体的には、脂肪族アミンとしては、例えば、トリメチルアミン、ジエチルアミン、トリエチルアミン、ジ－ｎ－プロピルアミン、トリ－ｎ－プロピルアミン、ジ－ｎ－ペンチルアミン、トリ－ｎ－ペンチルアミン、ジエタノールアミン、トリエタノールアミン、ジシクロヘキシルアミン、及び、ジシクロヘキシルメチルアミンなどが挙げられる。
　芳香族アミンとしては、例えば、アニリン、ベンジルアミン、Ｎ，Ｎ－ジメチルアニリン、及び、ジフェニルアミンなどが挙げられる。
　複素環式アミンとしては、例えば、ピリジン、２－メチルピリジン、４－メチルピリジン、２－エチルピリジン、４－エチルピリジン、２－フェニルピリジン、４－フェニルピリジン、Ｎ－メチル－４－フェニルピリジン、４－ジメチルアミノピリジン、イミダゾール、ベンズイミダゾール、４－メチルイミダゾール、２－フェニルベンズイミダゾール、２，４，５－トリフェニルイミダゾール、ニコチン、ニコチン酸、ニコチン酸アミド、キノリン、８－オキシキノリン、ピラジン、ピラゾール、ピリダジン、プリン、ピロリジン、ピペリジン、ピペラジン、モルホリン、４－メチルモルホリン、１，５－ジアザビシクロ［４．３．０］－５－ノネン、及び、１，８－ジアザビシクロ［５．３．０］－７－ウンデセンなどが挙げられる。
　第四級アンモニウムヒドロキシドとしては、例えば、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラ－ｎ－ブチルアンモニウムヒドロキシド、及び、テトラ－ｎ－ヘキシルアンモニウムヒドロキシドなどが挙げられる。
　カルボン酸の第四級アンモニウム塩としては、例えば、テトラメチルアンモニウムアセテート、テトラメチルアンモニウムベンゾエート、テトラ－ｎ－ブチルアンモニウムアセテート、及び、テトラ－ｎ－ブチルアンモニウムベンゾエートなどが挙げられる。 Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, and 1,8-diazabicyclo [5.3.0] -7-Undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
　上記塩基性化合物は、１種単独で使用しても、２種以上を併用してもよい。
　上記感光性樹脂層は、塩基性化合物を含まないか、塩基性化合物の含有量が、上記感光性樹脂層の全質量に対して、０質量％を超え２質量％以下であることが好ましく、塩基性化合物を含まないか、塩基性化合物の含有量が、上記感光性樹脂層の全質量に対して、０質量％を超え２質量％以下であることが好ましく、塩基性化合物を含まないか、塩基性化合物の含有量が、上記感光性樹脂層の全質量に対して、０質量％を超え１．２質量％以下であることがより好ましく、塩基性化合物を含まないことが特に好ましい。 The said basic compound may be used individually by 1 type, or may use 2 or more types together.
The photosensitive resin layer does not contain a basic compound, or the content of the basic compound is preferably more than 0% by mass and 2% by mass or less based on the total mass of the photosensitive resin layer. Whether the basic compound is not included, or the content of the basic compound is preferably more than 0% by mass and 2% by mass or less with respect to the total mass of the photosensitive resin layer, and does not include the basic compound More preferably, the content of the basic compound is more than 0% by mass and 1.2% by mass or less, and particularly preferably no basic compound, with respect to the total mass of the photosensitive resin layer.
＜＜その他の添加剤＞＞
　本開示における上記感光性樹脂層は、上記成分以外にも、必要に応じて公知の添加剤を含むことができる。 << Other additives >>
The said photosensitive resin layer in this indication can contain a well-known additive as needed besides the said component.
－界面活性剤－
　上記感光性樹脂層は、膜厚均一性の観点から界面活性剤を含有することが好ましい。界面活性剤としては、アニオン系、カチオン系、ノニオン系（非イオン系）、又は、両性のいずれでも使用することができるが、好ましい界面活性剤はノニオン界面活性剤である。
　ノニオン系界面活性剤の例としては、ポリオキシエチレン高級アルキルエーテル類、ポリオキシエチレン高級アルキルフェニルエーテル類、ポリオキシエチレングリコールの高級脂肪酸ジエステル類、シリコーン系、フッ素系界面活性剤を挙げることができる。また、以下商品名で、ＫＰ（信越化学工業（株）製）、ポリフロー（共栄社化学（株）製）、エフトップ（ＪＥＭＣＯ社製）、メガファック（ＤＩＣ（株）製）、フロラード（住友スリーエム（株）製）、アサヒガード、サーフロン（旭硝子（株）製）、ＰｏｌｙＦｏｘ（ＯＭＮＯＶＡ社製）、及び、ＳＨ－８４００（東レ・ダウコーニング（株）製）等の各シリーズを挙げることができる。
　また、界面活性剤として、下記式Ｉ－１で表される構成単位Ａ及び構成単位Ｂを含み、テトラヒドロフラン（ＴＨＦ）を溶剤とした場合のゲルパーミエーションクロマトグラフィーで測定されるポリスチレン換算の重量平均分子量（Ｍｗ）が１，０００以上１０，０００以下である共重合体を好ましい例として挙げることができる。 -Surfactant-
The photosensitive resin layer preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, nonionic (nonionic), or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . The following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFuck (manufactured by DIC Corporation), and Florard (Sumitomo 3M). Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (manufactured by Toray Dow Corning Co., Ltd.).
Further, as a surfactant, it contains a structural unit A and a structural unit B represented by the following formula I-1, and is a weight average in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A preferable example is a copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（Ｉ－１）中、Ｒ４０１及びＲ４０３はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ４０２は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ４０４は水素原子又は炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐ及びｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｓは１以上１０以下の整数を表し、＊は他の構造との結合部位を表す。 In formula (I-1), 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, and R 404 represents a hydrogen atom or a carbon group. Represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is a numerical value of 10 mass% to 80 mass%. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, s represents an integer of 1 to 10, and * represents a bonding site with another structure. Represent.
　Ｌは、下記式（Ｉ－２）で表される分岐アルキレン基であることが好ましい。式（Ｉ－２）におけるＲ４０５は、炭素数１以上４以下のアルキル基を表し、相溶性と被塗布面に対する濡れ性の点で、炭素数１以上３以下のアルキル基が好ましく、炭素数２又は３のアルキル基がより好ましい。ｐとｑとの和（ｐ＋ｑ）は、ｐ＋ｑ＝１００、すなわち、１００質量％であることが好ましい。 L is preferably a branched alkylene group represented by the following formula (I-2). R 405 in formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred. The sum of p and q (p + q) is preferably p + q = 100, that is, 100% by mass.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　共重合体の重量平均分子量（Ｍｗ）は、１，５００以上５，０００以下がより好ましい。 The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
　その他、特許第４５０２７８４号公報の段落００１７、特開２００９－２３７３６２号公報の段落００６０～段落００７１に記載の界面活性剤も用いることができる。 In addition, surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362 can also be used.
　界面活性剤は、１種単独で用いてもよく、２種以上を併用してもよい。
　界面活性剤の添加量は、上記感光性樹脂層の全質量に対して、１０質量％以下であることが好ましく、０．００１質量％～１０質量％であることがより好ましく、０．０１質量％～３質量％であることが更に好ましい。 Surfactant may be used individually by 1 type and may use 2 or more types together.
The addition amount of the surfactant is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and 0.01% by mass with respect to the total mass of the photosensitive resin layer. More preferably, the content is from 3% to 3% by mass.
－重合禁止剤－
　上記感光性樹脂層は、重合禁止剤を少なくとも１種含有してもよい。
　重合禁止剤としては、例えば、特許第４５０２７８４号公報の段落００１８に記載された熱重合防止剤を用いることができる。
　中でも、フェノチアジン、フェノキサジン又は４－メトキシフェノールを好適に用いることができる。 -Polymerization inhibitor-
The photosensitive resin layer may contain at least one polymerization inhibitor.
As the polymerization inhibitor, for example, the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784 can be used.
Of these, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.
　上記感光性樹脂層が重合禁止剤を含有する場合、重合禁止剤の含有量は、上記感光性樹脂層の全質量に対して、０．０１質量％～３質量％が好ましく、０．０１質量％～１質量％がより好ましく、０．０１質量％～０．８質量％が更に好ましい。 When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, and 0.01% by mass with respect to the total mass of the photosensitive resin layer. % To 1% by mass is more preferable, and 0.01% to 0.8% by mass is even more preferable.
－溶剤－
　上記感光性樹脂層は、溶剤を含んでいてもよい。
　また、上記感光性樹脂層を形成する感光性樹脂組成物は、上記感光性樹脂層を容易に形成するため、一旦溶剤を含有させて感光性樹脂組成物の粘度を調節し、溶剤を含む感光性樹脂組成物を塗布及び乾燥して、上記感光性樹脂層を好適に形成することができる。
　本開示に使用される溶剤としては、公知の溶剤を用いることができる。溶剤としては、エチレングリコールモノアルキルエーテル類、エチレングリコールジアルキルエーテル類、エチレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類、プロピレングリコールジアルキルエーテル類、プロピレングリコールモノアルキルエーテルアセテート類、ジエチレングリコールジアルキルエーテル類、ジエチレングリコールモノアルキルエーテルアセテート類、ジプロピレングリコールモノアルキルエーテル類、ジプロピレングリコールジアルキルエーテル類、ジプロピレングリコールモノアルキルエーテルアセテート類、エステル類、ケトン類、アミド類、及び、ラクトン類等が例示できる。また、溶剤の具体例としては特開２０１１－２２１４９４号公報の段落０１７４～段落０１７８に記載の溶剤も挙げられ、これらの内容は本明細書に組み込まれる。 -solvent-
The photosensitive resin layer may contain a solvent.
In addition, the photosensitive resin composition for forming the photosensitive resin layer is a photosensitive resin composition containing a solvent by adjusting the viscosity of the photosensitive resin composition once by adding a solvent in order to easily form the photosensitive resin layer. The photosensitive resin composition can be applied and dried to suitably form the photosensitive resin layer.
As the solvent used in the present disclosure, a known solvent can be used. Solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers And diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. Specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP2011-212494A, the contents of which are incorporated herein.
　また、既述の溶剤に、更に必要に応じて、ベンジルエチルエーテル、ジヘキシルエーテル、エチレングリコールモノフェニルエーテルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、イソホロン、カプロン酸、カプリル酸、１－オクタノール、１－ノナール、ベンジルアルコール、アニソール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジエチル、炭酸エチレン、又は、炭酸プロピレン等の溶剤を添加することもできる。
　溶剤は、１種のみ用いてもよく、２種以上を使用してもよい。
　本開示に用いることができる溶剤は、１種単独で用いてもよく、２種を併用することがより好ましい。溶剤を２種以上使用する場合には、例えば、プロピレングリコールモノアルキルエーテルアセテート類とジアルキルエーテル類との併用、ジアセテート類とジエチレングリコールジアルキルエーテル類との併用、又は、エステル類とブチレングリコールアルキルエーテルアセテート類との併用が好ましい。 In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, -Solvents such as nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate or propylene carbonate can also be added.
Only 1 type may be used for a solvent and 2 or more types may be used for it.
The solvent which can be used for this indication may be used individually by 1 type, and it is more preferable to use 2 types together. When two or more solvents are used, for example, combined use of propylene glycol monoalkyl ether acetates and dialkyl ethers, combined use of diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetates A combination with the above is preferred.
　また、溶剤としては、沸点１３０℃以上１６０℃未満の溶剤、沸点１６０℃以上の溶剤、又は、これらの混合物であることが好ましい。
　沸点１３０℃以上１６０℃未満の溶剤としては、プロピレングリコールモノメチルエーテルアセテート（沸点１４６℃）、プロピレングリコールモノエチルエーテルアセテート（沸点１５８℃）、プロピレングリコールメチル－ｎ－ブチルエーテル（沸点１５５℃）、及び、プロピレングリコールメチル－ｎ－プロピルエーテル（沸点１３１℃）が例示できる。
　沸点１６０℃以上の溶剤としては、３－エトキシプロピオン酸エチル（沸点１７０℃）、ジエチレングリコールメチルエチルエーテル（沸点１７６℃）、プロピレングリコールモノメチルエーテルプロピオネート（沸点１６０℃）、ジプロピレングリコールメチルエーテルアセテート（沸点２１３℃）、３－メトキシブチルエーテルアセテート（沸点１７１℃）、ジエチレングリコールジエチエルエーテル（沸点１８９℃）、ジエチレングリコールジメチルエーテル（沸点１６２℃）、プロピレングリコールジアセテート（沸点１９０℃）、ジエチレングリコールモノエチルエーテルアセテート（沸点２２０℃）、ジプロピレングリコールジメチルエーテル（沸点１７５℃）、及び、１，３－ブチレングリコールジアセテート（沸点２３２℃）が例示できる。 Further, the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), and An example is propylene glycol methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Bp 213 ° C), 3-methoxybutyl ether acetate (bp 171 ° C), diethylene glycol diethyl ether (bp 189 ° C), diethylene glycol dimethyl ether (bp 162 ° C), propylene glycol diacetate (bp 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), and 1,3-butylene glycol diacetate (boiling point 232 ° C) There can be exemplified.
　感光性樹脂組成物を塗布する際における溶剤の含有量は、感光性樹脂組成物中の全固形分１００質量部あたり、５０質量部～１，９００質量部であることが好ましく、１００質量部～９００質量部であることがより好ましい。
　また、上記感光性樹脂層における溶剤の含有量は、上記感光性樹脂層の全質量に対し、２質量％以下であることが好ましく、１質量％以下であることがより好ましく、０．５質量％以下であることが更に好ましい。 The content of the solvent in applying the photosensitive resin composition is preferably 50 parts by weight to 1,900 parts by weight, preferably 100 parts by weight to 100 parts by weight of the total solid content in the photosensitive resin composition. More preferably, it is 900 parts by mass.
The content of the solvent in the photosensitive resin layer is preferably 2% by mass or less, more preferably 1% by mass or less, and more preferably 0.5% by mass with respect to the total mass of the photosensitive resin layer. % Or less is more preferable.
－可塑剤－
　上記感光性樹脂層は、可塑性を改良する目的で、可塑剤を含有してもよい。
　上記可塑剤は、上記ａ１又はａ２で示される重合体よりも重量平均分子量が小さいことが好ましい。
　可塑剤の重量平均分子量は、可塑性付与の観点から、５００以上１０，０００未満が好ましく、７００以上５，０００未満がより好ましく、８００以上４，０００未満が更に好ましい。
　可塑剤は、上記重合体と相溶して可塑性を発現する化合物であれば特に限定されないが、可塑性付与の観点から、可塑剤は、分子中にアルキレンオキシ基を有することが好ましい。可塑剤に含まれるアルキレンオキシ基は下記構造を有することが好ましい。 -Plasticizer-
The photosensitive resin layer may contain a plasticizer for the purpose of improving plasticity.
The plasticizer preferably has a weight average molecular weight smaller than that of the polymer represented by a1 or a2.
The weight average molecular weight of the plasticizer is preferably from 500 to less than 10,000, more preferably from 700 to less than 5,000, and still more preferably from 800 to 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 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.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　上記式中、Ｒは炭素数２～８のアルキル基であり、ｎは１～５０の整数を表し、＊は他の原子との結合部位を表す。 In the above formula, R represents an alkyl group having 2 to 8 carbon atoms, n represents an integer of 1 to 50, and * represents a bonding site with another atom.
　なお、例えば、上記構造のアルキレンオキシ基を有する化合物（「化合物Ｘ」とする。）であっても、化合物Ｘ、上記重合体及び光酸発生剤を混合して得た化学増幅ポジ型感光性樹脂組成物が、化合物Ｘを含まずに形成した化学増幅ポジ型感光性樹脂組成物に比べて可塑性が向上しない場合は、本開示における可塑剤には該当しない。例えば、任意に添加される界面活性剤は、一般に感光性樹脂組成物に可塑性をもたらす量で使用されることはないため、本明細書における可塑剤には該当しない。 For example, even a compound having an alkyleneoxy group having the above structure (referred to as “compound X”) is obtained by mixing compound X, the above polymer and a photoacid generator, and a chemically amplified positive photosensitive property. When plasticity does not improve compared with the chemically amplified positive photosensitive resin composition formed without containing compound X, the resin composition does not fall under the plasticizer in the present disclosure. For example, the optionally added surfactant is generally not used in an amount that brings plasticity to the photosensitive resin composition, and thus does not correspond to the plasticizer in the present specification.
　上記可塑剤としては、例えば、下記構造を有する化合物が挙げられるが、これらに限定されるものではない。 Examples of the plasticizer include, but are not limited to, compounds having the following structure.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　可塑剤の含有量は、密着性の観点から、上記感光性樹脂層の全質量に対して、１質量％～５０質量％であることが好ましく、２質量％～２０質量％であることがより好ましい。
　上記感光性樹脂層は、可塑剤を１種のみを含んでいてもよく、２種以上を含んでいてもよい。 The content of the plasticizer is preferably 1% by mass to 50% by mass and more preferably 2% by mass to 20% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of adhesion. preferable.
The said photosensitive resin layer may contain only 1 type of plasticizers, and may contain 2 or more types.
－増感剤－
　上記感光性樹脂層は、増感剤を更に含むことができる。
　増感剤は、活性光線を吸収して電子励起状態となる。電子励起状態となった増感剤は、光酸発生剤と接触して、電子移動、エネルギー移動、及び、発熱などの作用が生じる。これにより光酸発生剤は化学変化を起こして分解し、酸を生成する。
　増感剤を含有させることで、露光感度を向上させることができる。 -Sensitizer-
The photosensitive resin layer can further contain a sensitizer.
The sensitizer absorbs actinic rays and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid.
Exposure sensitivity can be improved by containing a sensitizer.
　増感剤としては、アントラセン誘導体、アクリドン誘導体、チオキサントン誘導体、クマリン誘導体、ベーススチリル誘導体、及び、ジスチリルベンゼン誘導体よりなる群からえらばれた化合物が好ましく、アントラセン誘導体がより好ましい。
　アントラセン誘導体としては、アントラセン、９，１０－ジブトキシアントラセン、９，１０－ジクロロアントラセン、２－エチル－９，１０－ジメトキシアントラセン、９－ヒドロキシメチルアントラセン、９－ブロモアントラセン、９－クロロアントラセン、９，１０－ジブロモアントラセン、２－エチルアントラセン、又は、９，１０－ジメトキシアントラセンが好ましい。 As the sensitizer, a compound selected from the group consisting of an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a base styryl derivative, and a distyrylbenzene derivative is preferable, and an anthracene derivative is more preferable.
Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 1,10-dibromoanthracene, 2-ethylanthracene, or 9,10-dimethoxyanthracene is preferred.
　上記増感剤としては、国際公開第２０１５／０９３２７１号の段落０１３９～段落０１４１に記載の化合物を挙げることができる。 Examples of the sensitizer include compounds described in paragraphs 0139 to 0141 of International Publication No. 2015/092731.
　増感剤の含有量は、上記感光性樹脂層の全質量に対して、０質量％～１０質量％であることが好ましく、０．１質量％～１０質量％であることがより好ましい。 The content of the sensitizer is preferably 0% by mass to 10% by mass and more preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer.
－ヘテロ環状化合物－
　本開示における感光性樹脂層は、ヘテロ環状化合物を含むことができる。
　本開示におけるヘテロ環状化合物には、特に制限はない。例えば、以下に述べる分子内にエポキシ基又はオキセタニル基を有する化合物、アルコキシメチル基含有ヘテロ環状化合物、その他、各種環状エーテル、環状エステル（ラクトン）などの含酸素モノマー、更には珪素、硫黄、リンなどのｄ電子をもつヘテロ環モノマー等を添加することができる。 -Heterocyclic compounds-
The photosensitive resin layer in the present disclosure can include a heterocyclic compound.
There is no restriction | limiting in particular in the heterocyclic compound in this indication. For example, the following compounds having an epoxy group or oxetanyl group in the molecule, alkoxymethyl group-containing heterocyclic compounds, other cyclic ethers, oxygen-containing monomers such as cyclic esters (lactones), silicon, sulfur, phosphorus, etc. Heterocyclic monomers having the following d electrons can be added.
　感光性樹脂層中におけるヘテロ環状化合物の添加量は、ヘテロ環状化合物を添加する場合には、上記感光性樹脂層の全質量に対し、０．０１質量％～５０質量％であることが好ましく、０．１質量％～１０質量％であることがより好ましく、１質量％～５質量％であることが更に好ましい。上記範囲であると、密着性及びエッチング耐性の観点で好ましい。ヘテロ環状化合物は１種のみを用いてもよく、２種以上を併用することもできる。 The addition amount of the heterocyclic compound in the photosensitive resin layer is preferably 0.01% by mass to 50% by mass with respect to the total mass of the photosensitive resin layer when the heterocyclic compound is added. The content is more preferably 0.1% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass. It is preferable in the said range from a viewpoint of adhesiveness and etching tolerance. Only 1 type may be used for a heterocyclic compound and it can also use 2 or more types together.
　分子内にエポキシ基を有する化合物の具体例としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂肪族エポキシ樹脂等を挙げることができる。 Specific examples of the compound having an epoxy group in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like.
　分子内にエポキシ基を有する化合物は市販品として入手できる。例えば、ＪＥＲ８２８、ＪＥＲ１００７、ＪＥＲ１５７Ｓ７０（三菱化学（株）製）、ＪＥＲ１５７Ｓ６５（（株）三菱ケミカルホールディングス製）など、特開２０１１－２２１４９４号公報の段落０１８９に記載の市販品などが挙げられる。
　その他の市販品として、ＡＤＥＫＡ　ＲＥＳＩＮ　ＥＰ－４０００Ｓ、同ＥＰ－４００３Ｓ、同ＥＰ－４０１０Ｓ、同ＥＰ－４０１１Ｓ（以上、（株）ＡＤＥＫＡ製）、ＮＣ－２０００、ＮＣ－３０００、ＮＣ－７３００、ＸＤ－１０００、ＥＰＰＮ－５０１、ＥＰＰＮ－５０２（以上、（株）ＡＤＥＫＡ製）、デナコールＥＸ－６１１、ＥＸ－６１２、ＥＸ－６１４、ＥＸ－６１４Ｂ、ＥＸ－６２２、ＥＸ－５１２、ＥＸ－５２１、ＥＸ－４１１、ＥＸ－４２１、ＥＸ－３１３、ＥＸ－３１４、ＥＸ－３２１、ＥＸ－２１１、ＥＸ－２１２、ＥＸ－８１０、ＥＸ－８１１、ＥＸ－８５０、ＥＸ－８５１、ＥＸ－８２１、ＥＸ－８３０、ＥＸ－８３２、ＥＸ－８４１、ＥＸ－９１１、ＥＸ－９４１、ＥＸ－９２０、ＥＸ－９３１、ＥＸ－２１２Ｌ、ＥＸ－２１４Ｌ、ＥＸ－２１６Ｌ、ＥＸ－３２１Ｌ、ＥＸ－８５０Ｌ、ＤＬＣ－２０１、ＤＬＣ－２０３、ＤＬＣ－２０４、ＤＬＣ－２０５、ＤＬＣ－２０６、ＤＬＣ－３０１、ＤＬＣ－４０２、ＥＸ－１１１，ＥＸ－１２１、ＥＸ－１４１、ＥＸ－１４５、ＥＸ－１４６、ＥＸ－１４７、ＥＸ－１７１、ＥＸ－１９２（以上ナガセケムテック製）、ＹＨ－３００、ＹＨ－３０１、ＹＨ－３０２、ＹＨ－３１５、ＹＨ－３２４、ＹＨ－３２５（以上、新日鐵住金化学（株）製）セロキサイド２０２１Ｐ、２０８１、２０００、３０００、ＥＨＰＥ３１５０、エポリードＧＴ４００、セルビナースＢ０１３４、Ｂ０１７７（（株）ダイセル製）などが挙げられる。
　分子内にエポキシ基を有する化合物は１種単独で用いてもよく、２種以上を併用してもよい。 A compound having an epoxy group in the molecule can be obtained as a commercial product. For example, JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Co., Ltd.), JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like, commercially available products described in paragraph 0189 of JP2011-221494A, and the like can be mentioned.
Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD- 1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX- 411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212 , EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX -121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192 (manufactured by Nagase Chemtech), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Celoxide 2021P, 2081, 2000, 3000, EHPE3150, Epolide GT400, Cellbiners B0134, B0177 (manufactured by Daicel Corporation), and the like.
The compound which has an epoxy group in a molecule | numerator may be used individually by 1 type, and may use 2 or more types together.
　分子内にエポキシ基を有する化合物の中でも、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂及び脂肪族エポキシ樹脂がより好ましく挙げられ、脂肪族エポキシ樹脂が特に好ましく挙げられる。 Among the compounds having an epoxy group in the molecule, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and aliphatic epoxy resin is particularly preferable.
　分子内にオキセタニル基を有する化合物の具体例としては、アロンオキセタンＯＸＴ－２０１、ＯＸＴ－２１１、ＯＸＴ－２１２、ＯＸＴ－２１３、ＯＸＴ－１２１、ＯＸＴ－２２１、ＯＸ－ＳＱ、ＰＮＯＸ（以上、東亞合成（株）製）を用いることができる。 Specific examples of compounds having an oxetanyl group in the molecule include Aron Oxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei Co., Ltd.) Can be used.
　また、オキセタニル基を含む化合物は、単独で又はエポキシ基を含む化合物と混合して使用することが好ましい。 In addition, the compound containing an oxetanyl group is preferably used alone or mixed with a compound containing an epoxy group.
　本開示における感光性樹脂層においては、ヘテロ環状化合物がエポキシ基を有する化合物であることが、エッチング耐性及び線幅安定性の観点から好ましい。 In the photosensitive resin layer according to the present disclosure, the heterocyclic compound is preferably a compound having an epoxy group from the viewpoint of etching resistance and line width stability.
－アルコキシシラン化合物－
　上記感光性樹脂層は、アルコキシシラン化合物を含有してもよい。アルコキシシラン化合物としては、トリアルコキシシラン化合物が好ましく挙げられる。
　アルコキシシラン化合物としては、例えば、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－グリシドキシプロピルトリアコキシシラン、γ－グリシドキシプロピルアルキルジアルコキシシラン、γ－メタクリロキシプロピルトリアルコキシシラン、γ－メタクリロキシプロピルアルキルジアルコキシシラン、γ－クロロプロピルトリアルコキシシラン、γ－メルカプトプロピルトリアルコキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリアルコキシシラン、ビニルトリアルコキシシランが挙げられる。これらのうち、γ－グリシドキシプロピルトリアルコキシシランやγ－メタクリロキシプロピルトリアルコキシシランがより好ましく、γ－グリシドキシプロピルトリアルコキシシランが更に好ましく、３－グリシドキシプロピルトリメトキシシランが特に好ましい。これらは１種単独又は２種以上を組み合わせて使用することができる。 -Alkoxysilane compounds-
The photosensitive resin layer may contain an alkoxysilane compound. Preferred examples of the alkoxysilane compound include trialkoxysilane compounds.
Examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used alone or in combination of two or more.
－その他の成分－
　本開示における感光性樹脂層には、金属酸化物粒子、酸化防止剤、分散剤、酸増殖剤、現像促進剤、導電性繊維、着色剤、熱ラジカル重合開始剤、熱酸発生剤、紫外線吸収剤、増粘剤、架橋剤、及び、有機又は無機の沈殿防止剤などの公知の添加剤を更に加えることができる。
　その他の成分の好ましい態様については特開２０１４－８５６４３号公報の段落０１６５～段落０１８４にそれぞれ記載があり、この公報の内容は本明細書に組み込まれる。 -Other ingredients-
The photosensitive resin layer in the present disclosure includes metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, and ultraviolet absorption. Known additives such as an agent, a thickener, a crosslinking agent, and an organic or inorganic suspending agent can be further added.
Preferred embodiments of the other components are described in JP-A-2014-85643, paragraphs 0165 to 0184, respectively, and the contents of this publication are incorporated herein.
＜＜感光性樹脂層の平均膜厚＞＞
　上記感光性樹脂層の平均膜厚は、転写性（ラミネート性）の観点から、１．０μｍ以上が好ましく、２．０μｍ以上がより好ましい。また、上記感光性樹脂層の平均膜厚は、製造適性の観点から、２０μｍ以下が好ましく、１５μｍ以下がより好ましい。 << Average film thickness of photosensitive resin layer >>
The average film thickness of the photosensitive resin layer is preferably 1.0 μm or more, and more preferably 2.0 μm or more, from the viewpoint of transferability (laminate). The average film thickness of the photosensitive resin layer is preferably 20 μm or less, more preferably 15 μm or less, from the viewpoint of production suitability.
＜＜感光性樹脂層の形成方法＞＞
　各成分、及び、溶剤を任意の割合でかつ任意の方法で混合し、撹拌溶解して感光性樹脂層を形成するための感光性樹脂組成物を調製することができる。例えば、各成分を、それぞれ予め溶剤に溶解させた溶液とした後、得られた溶液を所定の割合で混合して組成物を調製することもできる。以上のように調製した組成物は、孔径０．２μｍのフィルター等を用いてろ過した後に、使用に供することもできる。 << Method for Forming Photosensitive Resin Layer >>
A photosensitive resin composition for forming a photosensitive resin layer can be prepared by mixing each component and a solvent in an arbitrary ratio and by an arbitrary method, and dissolving by stirring. For example, it is possible to prepare a composition by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent. The composition prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.
　感光性樹脂組成物を仮支持体又は後述する中間層上に塗布し、乾燥させることで、仮支持体上に感光性樹脂層を有する本開示に係る感光性転写材料を得ることができる。
　塗布方法は特に限定されず、スリット塗布、スピン塗布、カーテン塗布、インクジェット塗布などの公知の方法で塗布することができる。
　なお、中間層上に後述のその他の層を形成した上に、感光性樹脂層を塗布することもできる。 The photosensitive transfer material according to the present disclosure having the photosensitive resin layer on the temporary support can be obtained by applying the photosensitive resin composition on the temporary support or an intermediate layer described later and drying the photosensitive resin composition.
The coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
In addition, the photosensitive resin layer can also be applied after forming other layers described later on the intermediate layer.
＜中間層＞
　本開示に係る感光性転写材料は、解像性、引き置き時間依存抑制性、中間層と感光性樹脂層との密着性及びパターン形成性の観点から、上記仮支持体と上記感光性樹脂層との間に、中間層を有することが好ましい。また、上記中間層は、バインダーを含むことが好ましい。 <Intermediate layer>
The photosensitive transfer material according to the present disclosure includes the temporary support and the photosensitive resin layer from the viewpoints of resolution, retention time dependency suppression, adhesion between the intermediate layer and the photosensitive resin layer, and pattern formation. It is preferable to have an intermediate layer between them. Moreover, it is preferable that the said intermediate | middle layer contains a binder.
＜＜バインダー＞＞
　バインダーは、水溶性又はアルカリ可溶性のバインダーであることが好ましく、水溶性又はアルカリ可溶性のポリマーであることがより好ましい。
　なお、本開示において、「水溶性」とは、２５℃においてｐＨ７．０の水への溶解度が０．１質量％以上であることを意味し、「アルカリ可溶性」とは、２５℃においてｐＨ８．５以上のアルカリ水溶液への溶解度が０．１質量％以上であることを意味する。
　また、上記「水溶性又はアルカリ可溶性であり」とは、水溶性か、アルカリ可溶性のいずれかであっても、水溶性かつアルカリ可溶性であってもよい。 << Binder >>
The binder is preferably a water-soluble or alkali-soluble binder, and more preferably a water-soluble or alkali-soluble polymer.
In the present disclosure, “water-soluble” means that the solubility in water at pH 7.0 is 0.1% by mass or more at 25 ° C., and “alkali-soluble” means pH 8. It means that the solubility in an alkaline aqueous solution of 5 or more is 0.1% by mass or more.
Further, the above “water-soluble or alkali-soluble” may be either water-soluble or alkali-soluble, or water-soluble and alkali-soluble.
　バインダーとしては、例えば、フェノールホルムアルデヒド樹脂、ｍ－クレゾールホルムアルデヒド樹脂、ｐ－クレゾールホルムアルデヒド樹脂、ｍ－／ｐ－混合クレゾールホルムアルデヒド樹脂、フェノール／クレゾール（ｍ－，ｐ－，又はｍ－／ｐ－混合のいずれでもよい）混合ホルムアルデヒド樹脂等のノボラック樹脂、ピロガロールアセトン樹脂、ポリヒドロキシスチレン樹脂、変性セルロース樹脂、ヒドロキシ基を有するアクリル樹脂（例えば、ヒドロキシアルキル（メタ）アクリレートの単独重合体又は共重合体）、デンプン類、グリコーゲン類、キチン類、アガロース類、カラギーナン類、プルラン類、アラビアガム、ソヤガム、ポリアミド樹脂、エポキシ樹脂、ポリアセタール樹脂、アクリル樹脂、ポリスチレン樹脂、ポリウレタン樹脂、ポリビニルアルコール、ポリビニルホルマール、ポリアミド樹脂、ポリエステル樹脂、ポリエチレンイミン、ポリアリルアミン、ポリアルキレングリコール等が挙げられる。 Examples of the binder include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, or m- / p-mixed). Any may be used) novolak resin such as mixed formaldehyde resin, pyrogallol acetone resin, polyhydroxystyrene resin, modified cellulose resin, acrylic resin having a hydroxy group (for example, hydroxyalkyl (meth) acrylate homopolymer or copolymer), Starches, glycogens, chitins, agaroses, carrageenans, pullulans, gum arabic, soya gum, polyamide resin, epoxy resin, polyacetal resin, acrylic resin, polystyrene resin, polyester Urethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyethyleneimine, polyallylamine, polyalkylene glycol, and the like.
　これらの中でも、バインダーとしては、中間層と感光性樹脂層との密着性及びパターン形成性の観点から、ノボラック樹脂、変性セルロース樹脂及びヒドロキシ基を有するアクリル樹脂よりなる群から選ばれる少なくとも１種の樹脂であることが好ましく、変性セルロース樹脂及びヒドロキシ基を有するアクリル樹脂よりなる群から選ばれる少なくとも１種の樹脂であることがより好ましく、変性セルロース樹脂であることが更に好ましい。
　また、変性セルロース樹脂としては、中間層と感光性樹脂層との密着性及びパターン形成性の観点から、ヒドロキシアルキル化セルロースが好ましい。
　ヒドロキシアルキル化セルロースとしては、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ポリヒドロキシエチル化セルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、グリオキザール化ヒドロキシプロピルメチルセルロース、ヒドロキシプロピルメチルセルロースフタレート等が好ましく挙げられる。
　中でも、中間層と感光性樹脂層との密着性及びパターン形成性の観点から、ヒドロキシプロピルセルロース及びヒドロキシプロピルメチルセルロースよりなる群から選ばれる少なくとも１種の樹脂であることが好ましく、ヒドロキシプロピルメチルセルロースであることがより好ましい。
　また、バインダーとしては、中間層と感光性樹脂層との密着性の観点から、ポリビニルアルコール、及び、ポリビニルホルマールよりなる群から選ばれる少なくとも１種の樹脂であることが好ましく、ポリビニルアルコールであることがより好ましい。 Among these, the binder is at least one selected from the group consisting of a novolak resin, a modified cellulose resin, and an acrylic resin having a hydroxy group from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation. It is preferably a resin, more preferably at least one resin selected from the group consisting of a modified cellulose resin and an acrylic resin having a hydroxy group, and more preferably a modified cellulose resin.
The modified cellulose resin is preferably hydroxyalkylated cellulose from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation.
Preferred examples of the hydroxyalkylated cellulose include hydroxymethylcellulose, hydroxyethylcellulose, polyhydroxyethylated cellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, glyoxalized hydroxypropylmethylcellulose, hydroxypropylmethylcellulose phthalate and the like.
Among these, from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer and pattern formability, it is preferably at least one resin selected from the group consisting of hydroxypropylcellulose and hydroxypropylmethylcellulose, and is hydroxypropylmethylcellulose. It is more preferable.
In addition, the binder is preferably at least one resin selected from the group consisting of polyvinyl alcohol and polyvinyl formal from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, and is polyvinyl alcohol. Is more preferable.
　バインダーの重量平均分子量は、中間層と感光性樹脂層との密着性、パターン形成性、露光後の現像液への溶解性及び転写性の観点から、１，０００以上であることが好ましく、２，０００～１００，０００であることが好ましく、１０，０００～５０，０００であることがより好ましい。 The weight average molecular weight of the binder is preferably 1,000 or more from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer, pattern formation, solubility in the developer after exposure, and transferability. , Preferably from 100,000 to 100,000, more preferably from 10,000 to 50,000.
　上記中間層は、バインダーを１種単独で含有していても、２種以上を含有していてもよい。
　中間層中のバインダーの含有量は、中間層と感光性樹脂層との密着性、パターン形成性、露光後の現像液への溶解性及び転写性の観点から、中間層の全質量に対し、１０質量％以上１００質量％以下であることが好ましく、２０質量％以上１００質量％以下であることがより好ましく、４０質量％以上１００質量％以下であることが更に好ましく、６５質量％以上８５質量％以下であることが特に好ましい。 The said intermediate | middle layer may contain the binder individually by 1 type, or may contain 2 or more types.
The content of the binder in the intermediate layer is based on the adhesiveness between the intermediate layer and the photosensitive resin layer, pattern formation, solubility in the developer after exposure, and transferability, with respect to the total mass of the intermediate layer, It is preferably 10% by mass or more and 100% by mass or less, more preferably 20% by mass or more and 100% by mass or less, still more preferably 40% by mass or more and 100% by mass or less, and 65% by mass or more and 85% by mass. % Or less is particularly preferable.
＜＜その他の添加剤＞＞
　本開示における上記中間層は、バインダーに加え、必要に応じて公知の添加剤を含むことができる。
　その他の添加剤としては、上記感光性樹脂層に用いられるその他の添加剤が好適に挙げられる。 << Other additives >>
The intermediate layer in the present disclosure may contain a known additive as required in addition to the binder.
As other additives, other additives used for the photosensitive resin layer are preferably exemplified.
＜＜粒子＞＞
　上記中間層は、中間層と感光性樹脂層との密着性の観点から、粒子を含有することが好ましい。
　上記粒子としては、中間層と感光性樹脂層との密着性の観点から、金属酸化物粒子、又は、有機粒子であることが好ましく、Ｓｉ、Ｔｉ及びＺｒよりなる群から選択される元素の酸化物粒子、又は、有機粒子であることがより好ましい。
　なお、本開示における金属酸化物粒子の金属には、Ｂ、Ｓｉ、Ｇｅ、Ａｓ、Ｓｂ、Ｔｅ等の半金属も含まれるものとする。
　金属酸化物粒子としては、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｇｄ、Ｔｂ、Ｄｙ、Ｙｂ、Ｌｕ、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｍｏ、Ｗ、Ｚｎ、Ｂ、Ａｌ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉ、Ｔｅ等の原子を含む酸化物粒子が好ましく、シリカ、酸化チタン、チタン複合酸化物、酸化亜鉛、酸化ジルコニウム、インジウム／スズ酸化物、又は、アンチモン／スズ酸化物がより好ましく、シリカ、酸化チタン、チタン複合酸化物、又は、酸化ジルコニウムが更に好ましく、シリカ、酸化チタン、又は、酸化ジルコニウムが特に好ましい。
　有機粒子としては、有機樹脂粒子が好ましく挙げられる。
　有機樹脂粒子としては例えば、アクリル酸、メタクリル酸、アクリル酸エステル、メタクリル酸エステル等のアクリル酸系モノマーの単独重合体及び共重合体、ニトロセルロース、メチルセルロース、エチルセルロース、セルロースアセテートのようなセルロース系ポリマー、ポリエチレン、ポリプロピレン、ポリスチレン、塩化ビニル系共重合体、塩化ビニル－酢酸ビニル共重合体、ポリビニルピロリドン、ポリビニルブチラール、ポリビニルアルコールのようなビニル系ポリマー及びビニル化合物の共重合体、ポリエステル、ポリウレタン、ポリアミドのような縮合系ポリマー、ブタジエン－スチレン共重合体のようなゴム系熱可塑性ポリマー、エポキシ化合物のような光重合性若しくは熱重合性化合物を重合、架橋させたポリマー、メラミン化合物等を挙げることができる。
　これらの中でも、有機粒子としては、アクリル樹脂粒子が好ましく挙げられ、ポリメチルメタクリレート粒子がより好ましく挙げられる。
　また、これら粒子は、分散安定性付与のために表面を有機材料や無機材料で処理することもできる。上記粒子は、表面が親水性の粒子であることが好ましい。例えば、表面が疎水性の粒子の表面を親水化処理する等が挙げられる。 << Particles >>
The intermediate layer preferably contains particles from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer.
The above particles are preferably metal oxide particles or organic particles from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, and oxidation of an element selected from the group consisting of Si, Ti and Zr. More preferably, it is a physical particle or an organic particle.
Note that the metal of the metal oxide particles in the present disclosure includes semimetals such as B, Si, Ge, As, Sb, and Te.
The metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B , Oxide particles containing atoms such as Al, Si, Ge, Sn, Pb, Sb, Bi, Te, etc. are preferred, silica, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide, or Antimony / tin oxide is more preferable, silica, titanium oxide, titanium composite oxide, or zirconium oxide is more preferable, and silica, titanium oxide, or zirconium oxide is particularly preferable.
As the organic particles, organic resin particles are preferably exemplified.
Examples of the organic resin particles include homopolymers and copolymers of acrylic acid monomers such as acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, and cellulose polymers such as nitrocellulose, methylcellulose, ethylcellulose, and cellulose acetate. , Polyethylene, polypropylene, polystyrene, vinyl chloride copolymers, vinyl chloride-vinyl acetate copolymers, polyvinyl pyrrolidone, polyvinyl butyral, vinyl polymers such as polyvinyl alcohol, and copolymers of vinyl compounds, polyesters, polyurethanes, polyamides A condensation polymer such as butadiene-styrene copolymer, a rubber-based thermoplastic polymer such as a butadiene-styrene copolymer, a polymer obtained by polymerizing and crosslinking a photopolymerizable or thermopolymerizable compound such as an epoxy compound, Min compounds and the like.
Among these, acrylic resin particles are preferable as the organic particles, and polymethyl methacrylate particles are more preferable.
Moreover, the surface of these particles can be treated with an organic material or an inorganic material in order to impart dispersion stability. The particles are preferably particles having a hydrophilic surface. For example, the surface of particles having a hydrophobic surface may be subjected to a hydrophilic treatment.
　上記粒子の算術平均粒子径は、中間層と感光性樹脂層との密着性の観点から、４００ｎｍ以下であることが好ましく、２５０ｎｍ以下であることがより好ましく、１５０ｎｍ以下であることが更に好ましく、１０ｎｍ～２００ｎｍであることが特に好ましい。
　本開示における粒子の算術平均粒子径の測定方法は、電子顕微鏡により任意の粒子２００個の粒子径を測定し、その算術平均をいう。また、粒子の形状が球形でない場合には、最大径を径とする。 The arithmetic average particle diameter of the particles is preferably 400 nm or less, more preferably 250 nm or less, and further preferably 150 nm or less, from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer. A thickness of 10 nm to 200 nm is particularly preferable.
The method for measuring the arithmetic average particle diameter of the particles in the present disclosure refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the maximum diameter is the diameter.
　上記中間層における上記粒子の体積分率（中間層における粒子が占める体積割合）は、中間層と感光層との密着性の観点から、中間層の全体積に対し、５％～９０％であることが好ましく、１０％～８０％であることがより好ましく、１５％～７０％であることが更に好ましく、２０％～６０％であることが特に好ましい。 The volume fraction of the particles in the intermediate layer (volume ratio of particles in the intermediate layer) is 5% to 90% with respect to the total volume of the intermediate layer from the viewpoint of adhesion between the intermediate layer and the photosensitive layer. It is preferably 10% to 80%, more preferably 15% to 70%, and particularly preferably 20% to 60%.
＜＜中間層の平均膜厚＞＞
　上記中間層の平均膜厚は、中間層と感光性樹脂層との密着性、及び、パターン形成性の観点から、０．３μｍ～１０μｍが好ましく、０．３μｍ～５μｍがより好ましく、０．３μｍ～２μｍが特に好ましい。
　本開示における各層の平均膜厚の測定方法は、特に制限はなく、公知の方法を用いることができる。また、平均値は１０点以上測定し算出することが好ましい。
　具体的には例えば、表面形状測定や、断面の光学顕微鏡又は電子顕微鏡観察等が挙げられる。また、表面形状測定には、ブルカー社製Ｄｅｋｔａｋシリーズを好適に使用することができる。また、断面観察には、走査型電子顕微鏡（ＳＥＭ）を好適に用いることができる。
　また、上記中間層の厚みは、上記感光性樹脂層の厚みより薄いことが好ましい。 << Average thickness of intermediate layer >>
The average film thickness of the intermediate layer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and more preferably 0.3 μm from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formability. ˜2 μm is particularly preferred.
There is no restriction | limiting in particular in the measuring method of the average film thickness of each layer in this indication, A well-known method can be used. The average value is preferably measured and calculated at 10 points or more.
Specific examples include surface shape measurement and cross-sectional optical microscope or electron microscope observation. In addition, Bruker's Dektak series can be suitably used for surface shape measurement. Moreover, a scanning electron microscope (SEM) can be used suitably for cross-sectional observation.
Moreover, it is preferable that the thickness of the said intermediate | middle layer is thinner than the thickness of the said photosensitive resin layer.
＜＜中間層の形成方法＞＞
　中間層の形成方法は、特に制限はないが、各成分、及び、溶剤（好ましくは、水系溶剤）を所定の割合でかつ任意の方法で混合し、撹拌溶解して中間層を形成するための中間層形成用組成物を調製することができる。例えば、各成分を、それぞれ予め溶剤に溶解させた溶液とした後、得られた溶液を所定の割合で混合して組成物を調製することもできる。以上の如くして調製した組成物は、孔径５μｍのフィルター等を用いてろ過した後に、使用に供することもできる。
　水系溶剤としては、水や、アルコール類等の水溶性溶剤が挙げられる。 << Method for Forming Intermediate Layer >>
The method for forming the intermediate layer is not particularly limited, but each component and a solvent (preferably an aqueous solvent) are mixed at a predetermined ratio and in an arbitrary method, and stirred to dissolve to form the intermediate layer. An intermediate layer forming composition can be prepared. For example, it is possible to prepare a composition by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent. The composition prepared as described above can be used after being filtered using a filter having a pore diameter of 5 μm.
Examples of the aqueous solvent include water and water-soluble solvents such as alcohols.
　中間層形成用組成物を仮支持体に塗布し、乾燥させることで、仮支持体上に中間層を容易に形成することができる。
　塗布方法は特に限定されず、スリット塗布、スピン塗布、カーテン塗布、インクジェット塗布などの公知の方法で塗布することができる。
　なお、仮支持体上に後述のその他の層（例えば、熱可塑性樹脂層等）を形成した上に、中間層を塗布することもできる。 The intermediate layer can be easily formed on the temporary support by applying the intermediate layer-forming composition to the temporary support and drying it.
The coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
In addition, after forming other layers (for example, a thermoplastic resin layer or the like) described later on the temporary support, an intermediate layer can be applied.
＜その他の層＞
　本開示に係る感光性転写材料は、上記仮支持体、中間層及び感光性樹脂層以外の層（以下、「その他の層」と称することがある）を有していてもよい。その他の層としては、コントラストエンハンスメント層、カバーフィルム、熱可塑性樹脂層等を挙げることができる。 <Other layers>
The photosensitive transfer material according to the present disclosure may have a layer other than the temporary support, the intermediate layer, and the photosensitive resin layer (hereinafter sometimes referred to as “other layers”). Examples of other layers include a contrast enhancement layer, a cover film, and a thermoplastic resin layer.
－熱可塑性樹脂層、カバーフィルム等－
　本開示に係る感光性転写材料は、転写性の観点から、上記仮支持体と上記感光性樹脂層又は上記中間層との間に、熱可塑性樹脂層を更に有することが好ましい。
　また、本開示に係る感光性転写材料は、上記感光性樹脂層を保護する目的でカバーフィルムを有していてもよい。
　熱可塑性樹脂層の好ましい態様については特開２０１４－８５６４３号公報の段落０１８９～段落０１９３、他の層の好ましい態様については特開２０１４－８５６４３号公報の段落０１９４～段落０１９６にそれぞれ記載があり、この公報の内容は本明細書に組み込まれる。
　中でも、転写性の観点から、熱可塑性樹脂層が、アクリル樹脂及びスチレン／アクリル共重合体よりなる群から選ばれた少なくとも１種の熱可塑性樹脂を含むことが好ましい。 -Thermoplastic resin layer, cover film, etc.-
The photosensitive transfer material according to the present disclosure preferably further includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer or the intermediate layer from the viewpoint of transferability.
The photosensitive transfer material according to the present disclosure may have a cover film for the purpose of protecting the photosensitive resin layer.
Preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP 2014-85643 A, and preferred embodiments of the other layers are described in paragraphs 0194 to 0196 of JP 2014-85643 A, respectively. The contents of this publication are incorporated herein.
Especially, it is preferable that a thermoplastic resin layer contains the at least 1 sort (s) of thermoplastic resin chosen from the group which consists of an acrylic resin and a styrene / acryl copolymer from a transferable viewpoint.
　本開示に係る感光性転写材料が、熱可塑性樹脂層等のその他の層を有する場合、特開２００６－２５９１３８号公報の段落００９４～段落００９８に記載の感光性転写材料の作製方法に準じて作製することができる。
　例えば、熱可塑性樹脂層を有する本開示に係る感光性転写材料を作製する場合には、仮支持体上に、熱可塑性の有機高分子と添加剤とを溶解した溶解液（熱可塑性樹脂層用塗布液）を塗布し、乾燥させて熱可塑性樹脂層を設けた後、得られた熱可塑性樹脂層上に熱可塑性樹脂層を溶解しない溶剤に樹脂及び添加剤を加えて調製した調製液（中間層組成物）を塗布し、乾燥させて中間層を積層する。形成した中間層上に、更に、中間層を溶解しない溶剤を用いて調製した感光性樹脂組成物を塗布し、乾燥させて感光性樹脂層を積層することによって、本開示に係る感光性転写材料を好適に作製することができる。 When the photosensitive transfer material according to the present disclosure has other layers such as a thermoplastic resin layer, the photosensitive transfer material is manufactured according to the method for manufacturing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138. can do.
For example, when preparing a photosensitive transfer material according to the present disclosure having a thermoplastic resin layer, a solution (for thermoplastic resin layer) in which a thermoplastic organic polymer and an additive are dissolved on a temporary support. A coating solution prepared by adding a resin and an additive to a solvent that does not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer after applying a coating liquid) and drying to provide a thermoplastic resin layer (intermediate) The layer composition) is applied and dried to laminate the intermediate layer. A photosensitive transfer material according to the present disclosure is obtained by further applying a photosensitive resin composition prepared using a solvent that does not dissolve the intermediate layer on the formed intermediate layer, and drying and laminating the photosensitive resin layer. Can be suitably produced.
－コントラストエンハンスメント層－
　本開示に係る感光性転写材料は、上記感光性樹脂層に加え、コントラストエンハンスメント層を有することができる。
　コントラストエンハンスメント層（Ｃｏｎｔｒａｓｔ　Ｅｎｈａｎｃｅｍｅｎｔ　Ｌａｙｅｒ；ＣＥＬ）は、露光前には露光波長に対する吸収が大きいが、露光されるに伴って次第に吸収が小さくなる、すなわち、光の透過率が高くなる材料（光消色性色素成分と称する）を含有する層である。光消色性色素成分としては、ジアゾニウム塩、スチルバゾリウム塩、アリールニトロソ塩類等が知られている。被膜形成成分としては、フェノール系樹脂等が用いられる。
　その他、コントラストエンハンスメント層としては、特開平６－９７０６５号公報の段落０００４～段落００５１、特開平６－３３２１６７号公報の段落００１２～段落００５５、フォトポリマーハンドブック，フォトポリマー懇話会編，工業調査会（１９８９）、フォトポリマー・テクノロジー，山岡、永松編，（株）日刊工業新聞社（１９８８）に記載の材料を用いることができる。 -Contrast enhancement layer-
The photosensitive transfer material according to the present disclosure can have a contrast enhancement layer in addition to the photosensitive resin layer.
A contrast enhancement layer (CEL) is a material that absorbs light with respect to an exposure wavelength before exposure, but gradually decreases with exposure, that is, a material that increases light transmittance (photodecoloration). It is a layer containing a coloring pigment component). Known photodecolorable dye components include diazonium salts, stilbazolium salts, arylnitroso salts, and the like. A phenolic resin or the like is used as the film forming component.
In addition, as contrast enhancement layers, paragraphs 0004 to 0051 of JP-A-6-97065, paragraphs 0012 to 0055 of JP-A-6-332167, photopolymer handbook, photopolymer social gathering, industrial research group ( 1989), photopolymer technology, Yamaoka, Nagamatsu edition, Nikkan Kogyo Shimbun Co., Ltd. (1988) can be used.
（樹脂パターンの製造方法、及び、回路配線の製造方法）
　本開示に係る樹脂パターンの製造方法は、本開示に係る感光性転写材料を用いた樹脂パターンの製造方法であれば、特に制限はないが、本開示に係る感光性転写材料における上記感光性樹脂層を基板に接触させて貼り合わせる工程と、上記感光性樹脂層をパターン露光する工程と、露光された上記感光性樹脂層を現像してパターンを形成する工程と、をこの順に含み、上記基板に貼り合わせる工程の後、かつ上記パターンを形成する工程の前に、上記仮支持体を剥離する工程を含むことが好ましい。
　また、本開示に係る回路配線の製造方法は、本開示に係る感光性転写材料を用いた回路配線の製造方法であれば、特に制限はないが、本開示に係る感光性転写材料における上記感光性樹脂層を、導電層を有する基板に接触させて貼り合わせる工程と、上記感光性樹脂層をパターン露光する工程と、露光された上記感光性樹脂層を現像してパターンを形成する工程と、上記パターンが配置されていない領域における導電層をエッチング処理する工程と、をこの順に含み、上記基板に貼り合わせる工程の後、かつ上記パターンを形成する工程の前に、上記仮支持体を剥離する工程を含むことが好ましい。
　また、上記基板は、導電層を有する基板であることが好ましく、表面に導電層を有する基板であることがより好ましい。 (Resin pattern manufacturing method and circuit wiring manufacturing method)
The method for producing a resin pattern according to the present disclosure is not particularly limited as long as it is a method for producing a resin pattern using the photosensitive transfer material according to the present disclosure, but the photosensitive resin in the photosensitive transfer material according to the present disclosure. A step of bringing the layer into contact with the substrate and bonding, a step of pattern exposing the photosensitive resin layer, and a step of developing the exposed photosensitive resin layer to form a pattern, in this order, It is preferable to include the process of peeling the said temporary support body after the process of bonding together and before the process of forming the said pattern.
The circuit wiring manufacturing method according to the present disclosure is not particularly limited as long as it is a circuit wiring manufacturing method using the photosensitive transfer material according to the present disclosure. A step of bringing the photosensitive resin layer into contact with a substrate having a conductive layer, a step of pattern-exposing the photosensitive resin layer, a step of developing the exposed photosensitive resin layer to form a pattern, Etching the conductive layer in the region where the pattern is not disposed in this order, and after the step of bonding to the substrate and before the step of forming the pattern, the temporary support is peeled off It is preferable to include a process.
The substrate is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface.
　従来、感光性樹脂組成物は感光システムの違いから、活性光線を照射した部分が像として残るネガ型と、活性光線を照射していない部分を像として残すポジ型とに分けられる。ポジ型では活性光線を照射することにより、例えば活性光線を照射されて酸を発生する感光剤などを用いて露光部の溶解性を高めるため、パターン露光時点では露光部及び未露光部がいずれも硬化せず、得られたパターン形状が不良であった場合には全面露光などによって基板を再利用（リワーク）できる。そのため、いわゆるリワーク性に優れる観点からは、ポジ型が好ましい。また、残存した感光性樹脂層を再度露光して異なるパターンを作製する、という技術は感光性樹脂層でなければ実現できないため、本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法において、露光を２回以上行う態様が好ましく挙げられる。 Conventionally, photosensitive resin compositions are classified into a negative type in which a portion irradiated with actinic rays is left as an image and a positive type in which a portion not irradiated with actinic rays is left as an image due to differences in photosensitive systems. In the positive type, by irradiating actinic rays, for example, to improve the solubility of the exposed portion using a photosensitive agent that generates acid upon irradiation with actinic rays, both the exposed and unexposed portions are exposed at the time of pattern exposure. If the pattern shape obtained is not cured and the substrate is defective, the substrate can be reused (reworked) by full exposure or the like. Therefore, the positive type is preferable from the viewpoint of excellent so-called reworkability. Further, since the technique of reexposing the remaining photosensitive resin layer to produce a different pattern can be realized only by the photosensitive resin layer, the resin pattern manufacturing method according to the present disclosure or the circuit according to the present disclosure In the method for producing a wiring, an embodiment in which exposure is performed twice or more is preferable.
＜貼り合わせ工程＞
　本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法は、本開示に係る感光性転写材料における上記感光性樹脂層を、基板、好ましくは導電層を有する基板に接触させて貼り合わせる工程（貼り合わせ工程）を含むことが好ましい。
　また、上記貼り合わせ工程においては、上記導電層と、上記感光性樹脂層が接触するように圧着させることが好ましい。上記態様であると、露光及び現像後のパターン形成された感光性樹脂層を、導電層をエッチングする際のエッチングレジストとして好適に用いることができる。
　上記基板と上記感光性転写材料とを圧着する方法としては、特に制限はなく、公知の転写方法、及び、ラミネート方法を用いることができる。
　具体的には例えば、上記感光性転写材料の感光性樹脂層側を基板の上に重ね、ロール等による加圧、又は、加圧及び加熱することに行われることが好ましい。貼り合わせには、ラミネータ、真空ラミネータ、及び、より生産性を高めることができるオートカットラミネーター等の公知のラミネータを使用することができる。
　上記貼り合わせ工程における圧着圧力及び温度は、特に制限はなく、貼り合せる基板の表面の材質、例えば、導電層の材質、感光性樹脂層の材質、搬送速度、並びに、使用する圧着機等に応じ、適宜設定することができる。また、感光性転写材料の感光性樹脂層上にカバーフィルムを有する場合は、感光性樹脂層からカバーフィルムを除去した後、圧着すればよい。
　上記基材が樹脂フィルムである場合、ロールツーロールでの圧着を行ってもよい。 <Lamination process>
A method for manufacturing a resin pattern according to the present disclosure or a method for manufacturing a circuit wiring according to the present disclosure is provided by contacting the photosensitive resin layer in the photosensitive transfer material according to the present disclosure with a substrate, preferably a substrate having a conductive layer. It is preferable to include the process of bonding together (bonding process).
Moreover, in the said bonding process, it is preferable to make it pressure-bond so that the said conductive layer and the said photosensitive resin layer may contact. In the above embodiment, the patterned photosensitive resin layer after exposure and development can be suitably used as an etching resist when the conductive layer is etched.
There is no restriction | limiting in particular as a method of crimping | bonding the said board | substrate and the said photosensitive transfer material, A well-known transfer method and a lamination method can be used.
Specifically, for example, the photosensitive resin layer side of the photosensitive transfer material is preferably overlapped on a substrate and pressed by a roll or the like, or pressed and heated. For laminating, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
There are no particular limitations on the pressure and temperature of the bonding in the bonding step, and it depends on the surface material of the substrates to be bonded, for example, the material of the conductive layer, the material of the photosensitive resin layer, the conveyance speed, and the pressure bonding machine used. Can be set as appropriate. Moreover, what is necessary is just to crimp | bond, after removing a cover film from the photosensitive resin layer, when having a cover film on the photosensitive resin layer of a photosensitive transfer material.
When the base material is a resin film, a roll-to-roll pressure bonding may be performed.
　本開示に用いられる基板は、導電層を有する基板であることが好ましく、基材の表面に導電層を有する基板であることがより好ましい。導電層をパターンニングすることで配線を形成する。また、本開示においては、ポリエチレンテレフタレートなどのフィルム基材に金属酸化物や金属などの複数の導電層が設けられたものであることが好ましい。
　また、本開示に用いられる基板は、本開示における効果をより発揮する観点から、銅を含む基板であることが好ましい。また、本開示における効果をより発揮する観点から、上記導電層は、銅を含む層であることが好ましい。 The substrate used in the present disclosure is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface of a base material. A wiring is formed by patterning the conductive layer. Moreover, in this indication, it is preferable that several electroconductive layers, such as a metal oxide and a metal, were provided in film base materials, such as a polyethylene terephthalate.
Moreover, it is preferable that the board | substrate used for this indication is a board | substrate containing copper from a viewpoint which exhibits the effect in this indication more. Moreover, it is preferable that the said conductive layer is a layer containing copper from a viewpoint which exhibits the effect in this indication more.
　また、上記基板は、支持体上に複数の導電層が積層された基板であることが好ましい。
　支持体上に複数の導電層が積層された基板は、支持体がガラス基材又はフィルム基材であることが好ましく、フィルム基材であることがより好ましい。本開示に係る回路配線の製造方法は、タッチパネル用回路配線である場合、支持体がシート状樹脂組成物であることが特に好ましい。
　また、支持体は透明であることが好ましい。
　支持体の屈折率は、１．５０～１．５２であることが好ましい。
　支持体は、ガラス基材等の透光性基材で構成されていてもよく、コーニング社のゴリラガラスに代表される強化ガラスなどを用いることができる。また、上述の透明基材としては、特開２０１０－８６６８４号公報、特開２０１０－１５２８０９号公報及び特開２０１０－２５７４９２号公報に用いられている材料を好ましく用いることができる。
　基材としてフィルム基材を用いる場合は、光学的に歪みがない基材、及び、透明度が高い基材を用いることがより好ましく、具体的な素材には、ポリエチレンテレフタレート（ｐｏｌｙｅｔｈｙｌｅｎｅ　ｔｅｒｅｐｈｔｈａｌａｔｅ；ＰＥＴ）、ポリエチレンナフタレート、ポリカーボネート、トリアセチルセルロース、シクロオレフィンポリマーをあげることができる。 The substrate is preferably a substrate in which a plurality of conductive layers are stacked on a support.
As for the board | substrate with which the some electroconductive layer was laminated | stacked on the support body, it is preferable that a support body is a glass base material or a film base material, and it is more preferable that it is a film base material. When the circuit wiring manufacturing method according to the present disclosure is a touch panel circuit wiring, the support is particularly preferably a sheet-shaped resin composition.
The support is preferably transparent.
The refractive index of the support is preferably 1.50 to 1.52.
The support may be composed of a translucent substrate such as a glass substrate, and tempered glass represented by Corning's gorilla glass can be used. In addition, as the above-described transparent substrate, materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.
When a film substrate is used as the substrate, it is more preferable to use a substrate that is not optically distorted and a substrate having high transparency. Specific examples of the material include polyethylene terephthalate (PET), Examples thereof include polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.
　上記導電層としては、一般的な配線又はタッチパネル配線に用いられる任意の導電層を挙げることができる。
　導電層の材料としては、金属及び金属酸化物などを挙げることができる。
　金属酸化物としては、ＩＴＯ（Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ）、ＩＺＯ（Ｉｎｄｉｕｍ　Ｚｉｎｃ　Ｏｘｉｄｅ）、ＳｉＯ２等を挙げることができる。金属としては、Ａｌ、Ｚｎ、Ｃｕ、Ｆｅ、Ｎｉ、Ｃｒ、Ｍｏ等を挙げることができる。 Examples of the conductive layer include any conductive layer used for general wiring or touch panel wiring.
Examples of the material for the conductive layer include metals and metal oxides.
Examples of the metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO 2 . Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, and Mo.
　本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法は、上記複数の導電層のうち少なくとも一つの導電層が金属酸化物を含むことが好ましい。
　導電層としては、静電容量型タッチパネルに用いられる視認部のセンサーに相当する電極パターン又は周辺取り出し部の配線であることが好ましい。 In the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure, it is preferable that at least one of the plurality of conductive layers includes a metal oxide.
The conductive layer is preferably an electrode pattern corresponding to a sensor for a visual recognition part used in a capacitive touch panel or a wiring for a peripheral extraction part.
＜露光工程＞
　本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法は、上記貼り合わせる工程後、上記感光性樹脂層をパターン露光する工程（露光工程）を含むことが好ましい。
　上記露光工程では、上記感光性樹脂層を、所定のパターンを有するマスクを介して、活性光線を照射することが好ましい。この工程では、光酸発生剤が分解し酸が発生する。発生した酸の触媒作用により、塗膜成分中に含まれる酸分解性基が加水分解されて、酸基、例えば、カルボキシ基又はフェノール性水酸基が生成する。
　本開示において、パターンの詳細な配置及び具体的サイズは、特に限定されない。本開示において製造される回路基板を有する入力装置を備えた表示装置（例えば、タッチパネル）の表示品質を高め、また、取り出し配線の占める面積をできるだけ小さくしたいことから、パターンの少なくとも一部（特にタッチパネルの電極パターン及び取り出し配線の部分）は、１００μｍ以下の細線であることが好ましく、７０μｍ以下の細線であることがより好ましい。
　また、上記露光工程における露光は、マスクを介した露光でもよいし、レーザー等を用いたデジタル露光でもよいが、露光用マスクを介した露光であることが好ましい。
　本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法は、上記貼り合わせ工程と上記露光工程との間に、上記感光性転写材料と露光用マスクとを接触させる工程を含むことが好ましい。上記態様であると、得られるパターンの解像度により優れる。 <Exposure process>
It is preferable that the manufacturing method of the resin pattern which concerns on this indication, or the manufacturing method of the circuit wiring which concerns on this indication includes the process (exposure process) of carrying out pattern exposure of the said photosensitive resin layer after the said bonding process.
In the exposure step, the photosensitive resin layer is preferably irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to produce an acid group, for example, a carboxy group or a phenolic hydroxyl group.
In the present disclosure, the detailed arrangement and specific size of the pattern are not particularly limited. Since it is desired to improve the display quality of a display device (for example, a touch panel) including an input device having a circuit board manufactured in the present disclosure and to minimize the area occupied by the extraction wiring, at least a part of the pattern (particularly the touch panel) The electrode pattern and the part of the lead-out wiring) are preferably fine wires of 100 μm or less, and more preferably 70 μm or less.
The exposure in the exposure step may be exposure through a mask or digital exposure using a laser or the like, but is preferably exposure through an exposure mask.
The method for producing a resin pattern according to the present disclosure or the method for producing a circuit wiring according to the present disclosure includes a step of bringing the photosensitive transfer material and an exposure mask into contact between the bonding step and the exposure step. It is preferable to contain. It is excellent in the resolution of the pattern obtained as it is the said aspect.
　活性光線としては、可視光、紫外光、及び、電子線が挙げられるが、可視光又は紫外光が好ましく、紫外線が特に好ましい。
　活性光線による露光光源としては、低圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、発光ダイオード（ＬＥＤ）光源、エキシマレーザー発生装置などを用いることができ、ｇ線（４３６ｎｍ）、ｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）などの波長３００ｎｍ以上４５０ｎｍ以下の波長を有する活性光線が好ましく使用できる。また、必要に応じて長波長カットフィルター、短波長カットフィルター、バンドパスフィルターのような分光フィルターを通して照射光を調整することもできる。
　露光装置としては、ミラープロジェクションアライナー、ステッパー、スキャナー、プロキシミティ、コンタクト、マイクロレンズアレイ、レーザー露光など各種方式の露光機を用いることができる。
　露光量は、使用する感光性樹脂層に応じ、適宜選択すればよいが、５ｍＪ／ｃｍ２～２００ｍＪ／ｃｍ２であることが好ましく、１０ｍＪ／ｃｍ２～１００ｍＪ／ｃｍ２であることがより好ましい。
　また、露光後にパターンの矩形性、直線性を向上させる目的で、現像前に熱処理を行うことも好ましい。いわゆるＰＥＢ（Ｐｏｓｔ　Ｅｘｐｏｓｕｒｅ　Ｂａｋｅ）と呼ばれる工程により、露光時に感光性樹脂層中で生じた定在波によるパターンエッジの荒れを低減することが可能である。 Visible light, ultraviolet light, and an electron beam are mentioned as actinic light, However, Visible light or ultraviolet light is preferable and an ultraviolet-ray is especially preferable.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generator, etc. can be used. Actinic rays having a wavelength of 300 nm to 450 nm, such as h-line (405 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
Exposure dose, depending on the photosensitive resin layer to be used may be appropriately selected, but is preferably from 5mJ / cm 2 ~ 200mJ / cm 2, more preferably 10mJ / cm 2 ~ 100mJ / cm 2 .
It is also preferable to perform heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure. By a process called PEB (Post Exposure Bake), pattern edge roughness due to standing waves generated in the photosensitive resin layer during exposure can be reduced.
　なお、パターン露光は、仮支持体を感光性樹脂層から剥離してから行っても、仮支持体を剥離する前に、仮支持体を介して露光し、その後、仮支持体を剥離してもよい。なお、パターン露光は、マスクを介した露光でもよいし、レーザー等を用いたデジタル露光でもよい。 In addition, even if pattern exposure performs after peeling a temporary support body from the photosensitive resin layer, before peeling a temporary support body, it exposes through a temporary support body, and peels a temporary support body after that. Also good. The pattern exposure may be exposure through a mask or digital exposure using a laser or the like.
＜現像工程＞
　本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法は、上記露光する工程後、露光された上記感光性樹脂層を現像してパターンを形成する工程（現像工程）を含むことが好ましい。
　また、上記感光性転写材料が中間層を有する場合、現像工程においては、露光された部分の中間層も、露光された感光性樹脂層とともに除去される。
　更に、現像工程においては、未露光部の中間層も現像液に溶解あるいは分散する形で除去されてもよい。
　上記現像工程における露光された上記感光性樹脂層の現像は、現像液を用いて行うことができる。
　現像液としては、上記感光性樹脂層の露光部分を除去することができれば特に制限はなく、例えば、特開平５－７２７２４号公報に記載の現像液など、公知の現像液を使用することができる。なお、現像液は上記感光性樹脂層の露光部分が溶解型の現像挙動をする現像液が好ましい。現像液としては、アルカリ水溶液が好ましく、例えば、ｐＫａ＝７～１３の化合物を０．０５ｍｏｌ／Ｌ（リットル）～５ｍｏｌ／Ｌの濃度で含むアルカリ水溶液がより好ましい。現像液は、更に、水と混和性を有する有機溶剤、界面活性剤等を含有してもよい。本開示において好適に用いられる現像液としては、例えば、国際公開第２０１５／０９３２７１号の段落０１９４に記載の現像液が挙げられる。 <Development process>
The resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure includes a step of developing the exposed photosensitive resin layer to form a pattern after the exposing step (developing step). It is preferable to contain.
When the photosensitive transfer material has an intermediate layer, the exposed intermediate layer is also removed together with the exposed photosensitive resin layer in the development step.
Furthermore, in the development step, the intermediate layer in the unexposed area may also be removed in a form of being dissolved or dispersed in the developer.
Development of the exposed photosensitive resin layer in the development step can be performed using a developer.
The developer is not particularly limited as long as the exposed portion of the photosensitive resin layer can be removed. For example, a known developer such as the developer described in JP-A No. 5-72724 can be used. . The developer is preferably a developer in which the exposed portion of the photosensitive resin layer exhibits a dissolution type development behavior. The developer is preferably an alkaline aqueous solution, and more preferably, for example, an alkaline aqueous solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L. The developer may further contain an organic solvent miscible with water, a surfactant, and the like. Examples of the developer suitably used in the present disclosure include the developer described in Paragraph 0194 of International Publication No. 2015/092731.
　現像方式としては、特に制限はなくパドル現像、シャワー現像、シャワー及びスピン現像、ディップ現像等のいずれでもよい。ここで、シャワー現像について説明すると、露光後の感光性樹脂層に現像液をシャワーにより吹き付けることにより、露光部分を除去することができる。また、現像の後に、洗浄剤などをシャワーにより吹き付け、ブラシなどで擦りながら、現像残渣を除去することが好ましい。現像液の液温度は２０℃～４０℃が好ましい。
　また、露光から現像までの時間が長い態様であるほうが、本開示におけるパターン形状の変形を抑制する効果がより発揮される。露光後すぐ現像してもよいが、露光から現像までの時間が、露光から、好ましくは０．５時間以上、より好ましくは１時間以上、更に好ましく６時間以上経過した後、現像を行う態様において、本開示におけるパターン形状の変形を抑制する効果がより発揮される。
　また、本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法は、現像後、水等により洗浄する工程や、得られたパターンを有する基板を乾燥する工程等、公知の工程を含んでいてもよい。 The development method is not particularly limited, and any of paddle development, shower development, shower and spin development, dip development, and the like may be used. Here, the shower development will be described. The exposed portion can be removed by spraying the developer onto the exposed photosensitive resin layer by shower. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The liquid temperature of the developer is preferably 20 ° C. to 40 ° C.
Moreover, the effect which suppresses the deformation | transformation of the pattern shape in this indication is more exhibited in the aspect with long time from exposure to image development. Although development may be performed immediately after exposure, in a mode in which development is performed after the time from exposure to development is preferably 0.5 hours or more, more preferably 1 hour or more, and further preferably 6 hours or more after exposure. The effect of suppressing the deformation of the pattern shape in the present disclosure is further exhibited.
In addition, a method for manufacturing a resin pattern according to the present disclosure or a method for manufacturing a circuit wiring according to the present disclosure includes a step of washing with water after development, a step of drying a substrate having the obtained pattern, and the like. These steps may be included.
　更に、現像して得られたパターンを加熱処理するポストベーク工程を有していてもよい。
　ポストベークの加熱は８．１ｋＰａ～１２１．６ｋＰａの環境下で行うことが好ましく、５０．６６ｋＰａ以上の環境下で行うことがより好ましい。一方、１１１．４６ｋＰａ以下の環境下で行うことがより好ましく、１０１．３ｋＰａ以下の環境下で行うことが特に好ましい。
　ポストベークの温度は、８０℃～２５０℃であることが好ましく、１１０℃～１７０℃であることがより好ましく、１３０℃～１５０℃であることが特に好ましい。
　ポストベークの時間は、１分間～３０分間であることが好ましく、２分間～１０分間であることがより好ましく、２分間～４分間であることが特に好ましい。
　ポストベークは、空気環境下で行っても、窒素置換環境下で行ってもよい。 Furthermore, you may have the post-baking process which heat-processes the pattern obtained by image development.
The post-baking is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably in an environment of 50.66 kPa or more. On the other hand, it is more preferable to carry out in an environment of 111.46 kPa or less, and it is particularly preferable to carry out in an environment of 101.3 kPa or less.
The post-baking temperature is preferably 80 ° C. to 250 ° C., more preferably 110 ° C. to 170 ° C., and particularly preferably 130 ° C. to 150 ° C.
The post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
The post-bake may be performed in an air environment or a nitrogen substitution environment.
　本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法における各工程時における上記支持体の搬送速度は、特に制限はないが、露光時を除いて、０．５ｍ／ｍｉｎ～１０ｍ／ｍｉｎであることが好ましく、露光時を除いて、２．０ｍ／ｍｉｎ～８．０ｍ／ｍｉｎであることがより好ましい。 The transport speed of the support in each step of the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure is not particularly limited. It is preferably from min to 10 m / min, and more preferably from 2.0 m / min to 8.0 m / min except during exposure.
＜剥離工程＞
　本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法は、上記基板に貼り合わせる工程の後、かつ上記パターンを形成する工程の前に、上記仮支持体を剥離する工程（剥離工程）を含むことが好ましい。
　本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法は、上記感光性転写材料を用いるため、感光性転写材料を貼り合わせた後、かつ現像前のどのタイミングで仮支持体を剥離しても、感光性樹脂層との密着性に優れるため、一部剥がれ等の不良原因が生じることが抑制され、パターン形成を良好に行うことができる。
　また、本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法は、パターン形成性及び解像度の観点から、上記基板に貼り合わせる工程の後、かつ上記感光性樹脂層をパターン露光する工程の前に、上記仮支持体を剥離する工程を含むことがより好ましい。更に、上記態様であると、マスクを接触させてパターン露光する場合に、感光性樹脂層とマスクとが直接触れないため、パターン形成性及び解像度により優れる。
　上記剥離工程における仮支持体を剥離する方法は、特に制限はなく、公知の方法により剥離すればよい。 <Peeling process>
The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure peels off the temporary support after the step of bonding to the substrate and before the step of forming the pattern. It is preferable to include a process (peeling process).
The resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure uses the photosensitive transfer material. Therefore, after the photosensitive transfer material is bonded to each other and at any timing before development, Even if the support is peeled off, the adhesiveness with the photosensitive resin layer is excellent, so that the cause of defects such as partial peeling is suppressed, and the pattern can be formed satisfactorily.
In addition, the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure includes a step of bonding the substrate to the substrate and the photosensitive resin layer from the viewpoint of pattern formability and resolution. It is more preferable that a step of peeling the temporary support is included before the pattern exposure step. Further, in the case of the above-described aspect, when pattern exposure is performed with a mask in contact, the photosensitive resin layer and the mask are not in direct contact with each other, so that the pattern formability and resolution are excellent.
There is no restriction | limiting in particular in the method of peeling the temporary support body in the said peeling process, What is necessary is just to peel by a well-known method.
＜エッチング工程＞
　本開示に係る回路配線の製造方法は、上記パターンが配置されていない領域における導電層をエッチング処理する工程（エッチング工程）を含むことが好ましい。
　上記エッチング工程では、上記現像工程により上記感光性樹脂層から形成されたパターンを、エッチングレジストとして使用し、上記導電層のエッチング処理を行う。
　上記導電層のエッチングは、特開２０１０－１５２１５５号公報の段落００４８～段落００５４等に記載の方法、公知のプラズマエッチング等のドライエッチングによる方法など、公知の方法でエッチングを適用することができる。
　例えば、エッチングの方法としては、一般的に行われている、エッチング液に浸漬するウェットエッチング法が挙げられる。ウェットエッチングに用いられるエッチング液は、エッチングの対象に合わせて酸性タイプ又はアルカリ性タイプのエッチング液を適宜選択すればよい。
　酸性タイプのエッチング液としては、塩酸、硫酸、硝酸、酢酸、フッ酸、シュウ酸、又は、リン酸等の酸性成分単独の水溶液、酸性成分と塩化第２鉄、フッ化アンモニウム、又は、過マンガン酸カリウム等の塩の混合水溶液等が例示される。酸性成分は、複数の酸性成分を組み合わせた成分を使用してもよい。
　アルカリ性タイプのエッチング液としては、水酸化ナトリウム、水酸化カリウム、アンモニア、有機アミン、又は、テトラメチルアンモニウムハイドロオキサイドのような有機アミンの塩等のアルカリ成分単独の水溶液、アルカリ成分と過マンガン酸カリウム等の塩の混合水溶液等が例示される。アルカリ成分は、複数のアルカリ成分を組み合わせた成分を使用してもよい。 <Etching process>
The circuit wiring manufacturing method according to the present disclosure preferably includes a step (etching step) of etching the conductive layer in a region where the pattern is not disposed.
In the etching step, the conductive layer is etched using the pattern formed from the photosensitive resin layer in the developing step as an etching resist.
Etching of the conductive layer can be performed by a known method such as a method described in paragraphs 0048 to 0054 of JP 2010-152155 A or a dry etching method such as a known plasma etching.
For example, as an etching method, a commonly performed wet etching method in which the substrate is immersed in an etching solution can be used. As an etchant used for wet etching, an acid type or alkaline type etchant may be appropriately selected in accordance with an object to be etched.
Acidic etchants include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, aqueous solutions of acidic components such as phosphoric acid, acidic components and ferric chloride, ammonium fluoride, or permanganese Examples thereof include a mixed aqueous solution of a salt such as potassium acid. As the acidic component, a component obtained by combining a plurality of acidic components may be used.
Alkali type etching solutions include sodium hydroxide, potassium hydroxide, ammonia, organic amines, or aqueous solutions of alkali components such as organic amine salts such as tetramethylammonium hydroxide, alkaline components and potassium permanganate. A mixed aqueous solution of a salt such as As the alkali component, a component obtained by combining a plurality of alkali components may be used.
　エッチング液の温度は特に限定されないが、４５℃以下であることが好ましい。本開示において、エッチングマスク（エッチングパターン）として使用されるパターンは、４５℃以下の温度域における酸性及びアルカリ性のエッチング液に対して特に優れた耐性を発揮することが好ましい。したがって、エッチング工程中に上記パターンが剥離することが防止され、上記パターンの存在しない部分が選択的にエッチングされることになる。 The temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower. In the present disclosure, the pattern used as an etching mask (etching pattern) preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower. Therefore, the pattern is prevented from peeling off during the etching process, and a portion where the pattern does not exist is selectively etched.
　上記エッチング工程後、工程ラインの汚染を防ぐために、必要に応じて、エッチングされた上記基板を洗浄する工程（洗浄工程）、及び、エッチングされた上記基板を乾燥する工程（乾燥工程）を行ってもよい。洗浄工程については、例えば常温（１０℃～３５℃）で純水により１０秒～３００秒間基板を洗浄することが挙げられる。乾燥工程については、例えばエアブローを使用し、エアブロー圧（０．１ｋｇ／ｃｍ２～５ｋｇ／ｃｍ２程度）を適宜調整して乾燥を行えばよい。 After the etching process, in order to prevent contamination of the process line, a process of cleaning the etched substrate (cleaning process) and a process of drying the etched substrate (drying process) are performed as necessary. Also good. As for the cleaning step, for example, the substrate may be cleaned with pure water for 10 seconds to 300 seconds at room temperature (10 ° C. to 35 ° C.). Regarding the drying step, for example, air blow may be used, and the air blow pressure (about 0.1 kg / cm 2 to about 5 kg / cm 2 ) may be appropriately adjusted for drying.
＜エッチングレジスト剥離工程＞
　本開示に係る回路配線の製造方法は、上記エッチング工程の後に、上記感光性樹脂層を剥離液を用いて剥離する工程（エッチングレジスト剥離工程）を含むことが好ましい。
　上記エッチング工程の終了後、パターン形成された上記感光性樹脂層が残存している。上記感光性樹脂層が不要であれば、残存する全ての上記感光性樹脂層を除去すればよい。
　剥離液を用いて剥離する方法としては、例えば、好ましくは３０℃～８０℃、より好ましくは５０℃～８０℃にて撹拌中の剥離液に上記感光性樹脂層などを有する基材を５分～３０分間浸漬する方法が挙げられる。
　剥離液としては、例えば、水酸化ナトリウム若しくは水酸化カリウム等の無機アルカリ成分、又は、第三級アミン若しくは第四級アンモニウム塩等の有機アルカリ成分を、水、ジメチルスルホキシド、Ｎ－メチルピロリドン、又は、これらの混合溶液に溶解させた剥離液が挙げられる。剥離液を使用し、スプレー法、シャワー法、又は、パドル法等により剥離してもよい。 <Etching resist stripping process>
It is preferable that the manufacturing method of the circuit wiring which concerns on this indication includes the process (etching resist peeling process) which peels the said photosensitive resin layer using peeling liquid after the said etching process.
After the etching process is finished, the patterned photosensitive resin layer remains. If the photosensitive resin layer is unnecessary, all the remaining photosensitive resin layers may be removed.
As a method of peeling using a peeling solution, for example, a substrate having the above-mentioned photosensitive resin layer or the like in the peeling solution preferably stirred at 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 5 minutes. Examples include a method of immersing for ˜30 minutes.
As the stripping solution, for example, an inorganic alkali component such as sodium hydroxide or potassium hydroxide, or an organic alkali component such as a tertiary amine or quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or And a stripping solution dissolved in a mixed solution thereof. A stripping solution may be used and stripped by a spray method, a shower method, a paddle method, or the like.
　また、本開示に係る回路配線の製造方法は、必要に応じ、露光工程、現像工程及びエッチング工程を２回以上繰り返してもよい。
　本開示における露光工程、現像工程及びその他の工程の例としては、特開２００６－２３６９６号公報の段落００３５～段落００５１に記載の方法を、本開示においても好適に用いることができる。 Moreover, the manufacturing method of the circuit wiring which concerns on this indication may repeat an exposure process, a image development process, and an etching process twice or more as needed.
As examples of the exposure step, the development step, and other steps in the present disclosure, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present disclosure.
　本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法は、他の任意の工程を含んでもよい。例えば、以下のような工程が挙げられるが、これらの工程に限定されない。 The resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure may include other optional steps. For example, although the following processes are mentioned, it is not limited to these processes.
＜可視光線反射率を低下させる工程＞
　本開示に係る回路配線の製造方法は、導電層の表面、例えば、基板上に有する導電層の一部又は全ての表面の可視光線反射率を低下させる処理をする工程を含むことが可能である。
　可視光線反射率を低下させる処理としては、酸化処理などを挙げることができる。例えば、銅を酸化処理して酸化銅とすることで、黒化することにより、可視光線反射率を低下させることができる。
　可視光線反射率を低下させる処理の好ましい態様については、特開２０１４－１５０１１８号公報の段落００１７～段落００２５、並びに、特開２０１３－２０６３１５号公報の段落００４１、段落００４２、段落００４８及び段落００５８に記載があり、この公報の内容は本明細書に組み込まれる。 <Step of reducing visible light reflectance>
The manufacturing method of the circuit wiring according to the present disclosure may include a process of reducing the visible light reflectivity of the surface of the conductive layer, for example, a part or all of the surface of the conductive layer on the substrate. .
Examples of the treatment for reducing the visible light reflectance include an oxidation treatment. For example, the visible light reflectance can be reduced by blackening the copper by oxidizing copper.
Regarding preferred embodiments of the treatment for reducing the visible light reflectance, paragraphs 0017 to 0025 of JP2014-150118A, and paragraphs 0041, 0042, 0048 and 0058 of JP2013-206315A are described. The contents of this publication are incorporated herein.
＜エッチングされた上記基板上に絶縁膜を形成する工程、及び、絶縁膜上に新たな導電層を形成する工程＞
　本開示に係る回路配線の製造方法は、上記基板上、例えば、形成した配線（エッチングされた導電層）上に絶縁膜を形成する工程と、絶縁膜上に新たな導電層を形成する工程とを含むことも好ましい。
　絶縁膜を形成する工程については、特に制限はなく、公知の永久膜を形成する方法を挙げることができる。また、絶縁性を有する感光性材料を用いて、フォトリソグラフィにより所望のパターンの絶縁膜を形成してもよい。
　絶縁膜上に新たな導電層を形成する工程については、特に制限はない。導電性を有する感光性材料を用いて、フォトリソグラフィにより所望のパターンの新たな導電層を形成してもよい。 <Process for forming an insulating film on the etched substrate and process for forming a new conductive layer on the insulating film>
A method of manufacturing a circuit wiring according to the present disclosure includes a step of forming an insulating film on the substrate, for example, a formed wiring (etched conductive layer), and a step of forming a new conductive layer on the insulating film. It is also preferable to contain.
There is no restriction | limiting in particular about the process of forming an insulating film, The method of forming a well-known permanent film can be mentioned. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.
There is no particular limitation on the process of forming a new conductive layer on the insulating film. A new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
　また、本開示に係る回路配線の製造方法は、上記新たな導電層を、上記と同様な方法によりエッチングレジストを形成してエッチングしてもよいし、別途、公知の方法によりエッチングしてもよい。
　本開示に係る回路配線の製造方法により得られる回路配線を有する基板は、上記基板上に１層のみの配線を有していても、２層以上の配線を有していてもよい。 Further, in the method for manufacturing a circuit wiring according to the present disclosure, the new conductive layer may be etched by forming an etching resist by a method similar to the above, or may be separately etched by a known method. .
The substrate having the circuit wiring obtained by the circuit wiring manufacturing method according to the present disclosure may have only one layer of wiring on the substrate, or may have two or more layers of wiring.
　また、本開示に係る回路配線の製造方法は、基板が両方の表面にそれぞれ複数の導電層を有し、基板の両方の表面に形成された導電層に対して逐次又は同時に回路形成することも好ましい。このような構成により、基板の一方の表面に第一の導電パターン（第一の配線）、もう一方の表面に第二の導電パターン（第二の配線）を形成した配線、好ましくはタッチパネル用配線を形成することができる。 Further, in the method for manufacturing circuit wiring according to the present disclosure, the substrate may have a plurality of conductive layers on both surfaces, and the circuit may be sequentially or simultaneously formed on the conductive layers formed on both surfaces of the substrate. preferable. With such a configuration, a wiring in which a first conductive pattern (first wiring) is formed on one surface of the substrate and a second conductive pattern (second wiring) is formed on the other surface, preferably a touch panel wiring. Can be formed.
（回路配線、及び、回路配線を有する基板）
　本開示に係る回路配線は、本開示に係る回路配線の製造方法により製造された回路配線である。
　本開示に係る回路配線を有する基板は、本開示に係る回路配線の製造方法により製造された回路配線を有する基板である。
　本開示に係る回路配線を有する基板の用途は限定されないが、例えば、タッチパネル用回路配線基板であることが好ましい。 (Circuit wiring and substrate having circuit wiring)
The circuit wiring according to the present disclosure is a circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure.
The board | substrate which has the circuit wiring which concerns on this indication is a board | substrate which has the circuit wiring manufactured by the manufacturing method of the circuit wiring which concerns on this indication.
Although the use of the board | substrate which has the circuit wiring which concerns on this indication is not limited, For example, it is preferable that it is a circuit wiring board for touchscreens.
（入力装置及び表示装置）
　本開示に係る回路配線の製造方法により製造される回路配線を備えた装置として、入力装置が挙げられる。
　本開示に係る入力装置は、本開示に係る回路配線の製造方法により製造される回路配線を少なくとも有する入力装置であればよく、静電容量型タッチパネルであることが好ましい。
　本開示に係る表示装置は、本開示に係る入力装置を備えることが好ましい。本開示に係る表示装置は、有機ＥＬ表示装置、及び、液晶表示装置等の画像表示装置であることが好ましい。 (Input device and display device)
An input device is mentioned as an apparatus provided with the circuit wiring manufactured by the manufacturing method of the circuit wiring concerning this indication.
The input device according to the present disclosure may be an input device having at least a circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure, and is preferably a capacitive touch panel.
The display device according to the present disclosure preferably includes the input device according to the present disclosure. The display device according to the present disclosure is preferably an organic EL display device and an image display device such as a liquid crystal display device.
（タッチパネル、及び、タッチパネル表示装置）
　本開示に係るタッチパネルは、本開示に係る回路配線の製造方法により製造された回路配線を少なくとも有するタッチパネルである。また、本開示に係るタッチパネルは、透明基板と、電極と、絶縁層又は保護層とを少なくとも有することが好ましい。
　本開示に係るタッチパネル表示装置は、本開示に係る回路配線の製造方法により製造された回路配線を少なくとも有するタッチパネル表示装置であり、本開示に係るタッチパネルを有するタッチパネル表示装置であることが好ましい。
　また、本開示に係るタッチパネルの製造方法は、本開示に係る感光性転写材料を用いたタッチパネルの製造方法であれば、特に制限はないが、本開示に係る感光性転写材料の上記感光性樹脂層を、導電層を有する基板に接触させて貼り合わせる工程と、上記感光性樹脂層をパターン露光する工程と、露光された上記感光性樹脂層を現像してパターンを形成する工程と、上記パターンが配置されていない領域における導電層をエッチング処理する工程と、をこの順に含むことが好ましい。
　本開示に係るタッチパネル及び本開示に係るタッチパネル表示装置のおける検出方法としては、抵抗膜方式、静電容量方式、超音波方式、電磁誘導方式、及び、光学方式など公知の方式いずれでもよい。中でも、静電容量方式が好ましい。 (Touch panel and touch panel display device)
The touch panel according to the present disclosure is a touch panel having at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure. In addition, the touch panel according to the present disclosure preferably includes at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
The touch panel display device according to the present disclosure is a touch panel display device having at least circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure, and is preferably a touch panel display device including the touch panel according to the present disclosure.
Further, the touch panel manufacturing method according to the present disclosure is not particularly limited as long as it is a touch panel manufacturing method using the photosensitive transfer material according to the present disclosure, but the photosensitive resin of the photosensitive transfer material according to the present disclosure. A step of bringing a layer into contact with a substrate having a conductive layer, a step of pattern-exposing the photosensitive resin layer, a step of developing the exposed photosensitive resin layer to form a pattern, and the pattern It is preferable to include a step of etching the conductive layer in a region where no is disposed.
As a detection method in the touch panel according to the present disclosure and the touch panel display device according to the present disclosure, any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Among these, the electrostatic capacity method is preferable.
　タッチパネル型としては、いわゆる、インセル型（例えば、特表２０１２－５１７０５１号公報の図５、図６、図７、図８に記載のもの）、いわゆる、オンセル型（例えば、特開２０１３－１６８１２５号公報の図１９に記載のもの、特開２０１２－８９１０２号公報の図１や図５に記載のもの）、ＯＧＳ（Ｏｎｅ　Ｇｌａｓｓ　Ｓｏｌｕｔｉｏｎ）型、ＴＯＬ（Ｔｏｕｃｈ－ｏｎ－Ｌｅｎｓ）型（例えば、特開２０１３－５４７２７号公報の図２に記載のもの）、その他の構成（例えば、特開２０１３－１６４８７１号公報の図６に記載のもの）、各種アウトセル型（いわゆる、ＧＧ、Ｇ１・Ｇ２、ＧＦＦ、ＧＦ２、ＧＦ１、Ｇ１Ｆなど）を挙げることができる。 As the touch panel type, a so-called in-cell type (for example, those described in FIGS. 5, 6, 7, and 8 of JP-T-2012-517051), a so-called on-cell type (for example, JP 2013-168125 A). 19 of the gazette, those described in FIGS. 1 and 5 of JP 2012-89102 A, OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP No. 2013-54727 shown in FIG. 2), other configurations (for example, those shown in FIG. 6 of JP2013-164671A), various out-cell types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.).
　本開示に係るタッチパネル及び本開示に係るタッチパネル表示装置としては、“最新タッチパネル技術”（２００９年７月６日、（株）テクノタイムズ社発行）、三谷雄二監修、“タッチパネルの技術と開発”（２００４年１２月、シーエムシー出版）、ＦＰＤ　Ｉｎｔｅｒｎａｔｉｏｎａｌ　２００９　Ｆｏｒｕｍ　Ｔ－１１講演テキストブック、Ｃｙｐｒｅｓｓ　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ　Ｃｏｒｐｏｒａｔｉｏｎ　アプリケーションノートＡＮ２２９２等に開示されている構成を適用することができる。 As the touch panel according to the present disclosure and the touch panel display device according to the present disclosure, “latest touch panel technology” (issued July 6, 2009, published by Techno Times Co., Ltd.), supervised by Yuji Mitani, “touch panel technology and development” ( The configurations disclosed in FPD International 2009 Forum T-11 lecture textbook, Cypress Semiconductor Corporation application note AN2292, etc. can be applied.
　以下に実施例を挙げて本発明の実施形態を更に具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、及び、処理手順等は、本発明の実施形態の趣旨を逸脱しない限り、適宜、変更することができる。したがって、本発明の実施形態の範囲は以下に示す具体例に限定されない。なお、特に断りのない限り、「部」、「％」は質量基準である。 Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the embodiment of the present invention. Therefore, the scope of the embodiment of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.
＜重合体成分＞
　以下の合成例、において、以下の略語はそれぞれ以下の化合物を表す。
　ＡＴＨＦ：２－テトラヒドロフラニルアクリレート（合成品）
　ＭＡＴＨＦ：２－テトラヒドロフラニルメタクリレート（合成品）
　ＴＢＡ：ｔｅｒｔ－ブチルアクリレート（富士フイルム和光純薬（株）製）
　ＡＡ：アクリル酸（富士フイルム和光純薬（株）製）
　ＥＡ：アクリル酸エチル（富士フイルム和光純薬（株）製）
　ＭＭＡ：メタクリル酸メチル（富士フイルム和光純薬（株）製）
　ＣＨＡ：アクリル酸シクロヘキシル（富士フイルム和光純薬（株）製）
　ＢＭＡ：メタクリル酸ベンジル（富士フイルム和光純薬（株）製）
　ＰＭＰＭＡ：メタクリル酸１，２，２，６，６－ペンタメチル－４－ピペリジル（富士フイルム和光純薬（株）製）
　ＤＭＡＰＡＡ：Ｎ－［３－（ジメチルアミノ）プロピル］アクリルアミド（富士フイルム和光純薬（株）製）
　ＤＭＡＥＭＡ：メタクリル酸２－（ジメチルアミノ）エチル（富士フイルム和光純薬（株）製）
　ＤＥＡＥＭＡ：メタクリル酸２－（ジエチルアミノ）エチル（富士フイルム和光純薬（株）製）
　ＤＰＡＥＭＡ：メタクリル酸２－（ジイソプロピルアミノ）エチル（富士フイルム和光純薬（株）製）
　ＭＥＭＡ：メタクリル酸２－モルホリノエチル（東京化成工業（株）製）
　ＶＰ：ビニルピリジン（富士フイルム和光純薬（株）製）
　ＶＩ：１－ビニルイミダゾール（東京化成工業（株）製）
　ＶＴ：１－ビニル－１，２，４－トリアゾール（シグマ－アルドリッチ社製）
　ＮＶＰ：Ｎ－ビニルピロリドン（富士フイルム和光純薬（株）製）
　ＤＭＡＡ：ジメチルアクリルアミド（富士フイルム和光純薬（株）製）
　ＭＡＮａ：メタクリル酸ナトリウム（富士フイルム和光純薬（株）製）
　ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート（昭和電工（株）製）
　Ｖ－６０１：ジメチル　２，２’－アゾビス（２－メチルプロピオネート）（富士フイルム和光純薬（株）製） <Polymer component>
In the following synthesis examples, the following abbreviations represent the following compounds, respectively.
ATHF: 2-tetrahydrofuranyl acrylate (synthetic product)
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
TBA: tert-butyl acrylate (Fuji Film Wako Pure Chemical Industries, Ltd.)
AA: Acrylic acid (Fuji Film Wako Pure Chemical Industries, Ltd.)
EA: ethyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (Fuji Film Wako Pure Chemical Industries, Ltd.)
CHA: cyclohexyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
BMA: benzyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
PMPMA: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
DMAPAA: N- [3- (dimethylamino) propyl] acrylamide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
DMAEMA: 2- (dimethylamino) ethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
DEAEMA: 2- (diethylamino) ethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
DPAEMA: 2- (diisopropylamino) ethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
MEMA: 2-morpholinoethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
VP: Vinylpyridine (Fuji Film Wako Pure Chemical Industries, Ltd.)
VI: 1-vinylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
VT: 1-vinyl-1,2,4-triazole (manufactured by Sigma-Aldrich)
NVP: N-vinylpyrrolidone (Fuji Film Wako Pure Chemical Industries, Ltd.)
DMAA: Dimethylacrylamide (Fujifilm Wako Pure Chemical Industries, Ltd.)
MANa: sodium methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko KK)
V-601: Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
＜ＡＴＨＦの合成＞
　３つ口フラスコにアクリル酸（７２．１質量部、１．０モル当量）、ヘキサン（７２．１質量部）を加え２０℃に冷却した。カンファースルホン酸（０．００７０質量部、０．０３ミリモル当量）、２－ジヒドロフラン（７７．９質量部、１．０モル当量）を滴下した後に、２０℃±２℃の範囲内で１．５時間撹拌した後、３５℃まで昇温して２時間撹拌した。ヌッチェにキョーワード２００（ろ過材、水酸化アルミニウム粉末、協和化学工業（株）製）、キョーワード１０００（ろ過材、ハイドロタルサイト系粉末、協和化学工業（株）製）の順に敷き詰めた後、反応液をろ過することでろ過液を得た。得られたろ過液にヒドロキノンモノメチルエーテル（ＭＥＨＱ、０．００１２質量部）を加えた後、４０℃で減圧濃縮することで、アクリル酸テトラヒドロフラン－２－イル（ＡＴＨＦ）１４０．８質量部を無色油状物として得た（収率９９．０％）。 <Synthesis of ATHF>
Acrylic acid (72.1 parts by mass, 1.0 molar equivalent) and hexane (72.1 parts by mass) were added to a three-necked flask and cooled to 20 ° C. After adding camphor sulfonic acid (0.0070 parts by mass, 0.03 mmol equivalent) and 2-dihydrofuran (77.9 parts by mass, 1.0 mol equivalent), 1. within a range of 20 ° C. ± 2 ° C. After stirring for 5 hours, it heated up to 35 degreeC and stirred for 2 hours. After spreading Kyoward 200 (filter material, aluminum hydroxide powder, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (filter material, hydrotalcite-based powder, manufactured by Kyowa Chemical Industry Co., Ltd.) The reaction solution was filtered to obtain a filtrate. Hydroquinone monomethyl ether (MEHQ, 0.0012 parts by mass) was added to the obtained filtrate, followed by concentration under reduced pressure at 40 ° C., whereby 140.8 parts by mass of tetrahydrofuran-2-yl acrylate (ATHF) was a colorless oil. (Yield 99.0%).
＜ＭＡＴＨＦの合成＞
　アクリル酸をメタクリル酸に変更した以外は、ＡＴＨＦの合成と同様の等量比にして合成した。 <Synthesis of MATHF>
The synthesis was carried out with the same equivalent ratio as the synthesis of ATHF except that acrylic acid was changed to methacrylic acid.
＜重合体Ａ－１の合成例＞
　３つ口フラスコにＰＧＭＥＡ（７５．０質量部）を入れ、窒素雰囲気下において９０℃に昇温した。ＡＴＨＦ（３０．０質量部）、ＰＭＰＭＡ（１．０質量部）、アクリル酸エチル（ＥＡ、３５．０質量部）、メタクリル酸メチル（ＭＭＡ、３４．０質量部）、Ｖ－６０１（４．０質量部）、ＰＧＭＥＡ（７５．０質量部）を加えた溶液を、９０℃±２℃に維持した３つ口フラスコ溶液中に２時間かけて滴下した。滴下終了後、９０℃±２℃にて２時間撹拌することで、重合体Ａ－１（固形分濃度４０．０％）を得た。 <Synthesis Example of Polymer A-1>
PGMEA (75.0 parts by mass) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. ATHF (30.0 parts by mass), PMPMA (1.0 parts by mass), ethyl acrylate (EA, 35.0 parts by mass), methyl methacrylate (MMA, 34.0 parts by mass), V-601 (4. 0 parts by mass) and PGMEA (75.0 parts by mass) were added dropwise to the three-necked flask solution maintained at 90 ° C. ± 2 ° C. over 2 hours. After completion of the dropwise addition, the mixture was stirred at 90 ° C. ± 2 ° C. for 2 hours to obtain a polymer A-1 (solid content concentration 40.0%).
＜重合体Ａ－２～重合体Ａ－２３の合成例＞
　モノマーの種類等を下記表１に示す通りに変更し、その他の条件については、重合体Ａ－１と同様の方法で合成した。重合体の固形分濃度は４０質量％とした。表１における各モノマーの使用量の単位は、質量％である。 <Synthesis Example of Polymer A-2 to Polymer A-23>
The monomer type and the like were changed as shown in Table 1 below, and the other conditions were synthesized in the same manner as for Polymer A-1. The solid content concentration of the polymer was 40% by mass. The unit of the amount of each monomer used in Table 1 is mass%.
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
＜光酸発生剤＞
　Ｂ－１：下記に示す構造の化合物（特開２０１３－４７７６５号公報の段落０２２７に記載の化合物、段落０２２７に記載の方法に従って合成した。） <Photo acid generator>
B-1: Compound having the structure shown below (Compound described in paragraph 0227 of JP 2013-47765 A, synthesized according to the method described in paragraph 0227)
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　Ｂ－２：ＰＡＧ－１０３（商品名、ＢＡＳＦ社製、下記化合物） B-2: PAG-103 (trade name, manufactured by BASF, the following compound)
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　Ｂ－３：下記に示す構造の化合物（特開２０１４－１９７１５５号公報の段落０２１０に記載の方法に従って合成した。） B-3: Compound having the structure shown below (synthesized according to the method described in paragraph 0210 of JP-A-2014-197155)
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　上記化合物中、Ｔｓは、トシル基を表す。 In the above compounds, Ts represents a tosyl group.
　Ｂ－４：ＧＳＩＤ－２６－１、トリアリールスルホニウム塩（ＢＡＳＦ社製、下記化合物） B-4: GSID-26-1, triarylsulfonium salt (manufactured by BASF, the following compound)
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
＜界面活性剤＞
　Ｃ－１：下記に示す構造の化合物 <Surfactant>
C-1: Compound having the structure shown below
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
＜塩基性化合物＞
　Ｄ－１：下記に示す構造の化合物 <Basic compound>
D-1: Compound having the structure shown below
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　Ｄ－２：２－フェニルイミダゾール（東京化成工業（株）製）
　Ｄ－３：トリオクチルアミン（東京化成工業（株）製） D-2: 2-Phenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
D-3: Trioctylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
＜感光性転写材料の作製＞
　実施例１～１７及び比較例１～５では、下記表２に示す固形分比（質量比）となるように、重合体成分、光酸発生剤、塩基性化合物、及び、界面活性剤をＰＧＭＥＡに固形分濃度１０質量％になるように溶解混合し、孔径０．２μｍのポリテトラフルオロエチレン製フィルターで濾過して、感光性樹脂組成物をそれぞれ得た。
　各実施例及び比較例において、得られた感光性樹脂組成物を、仮支持体となる厚さ３０μｍのポリエチレンテレフタレートフィルム（以下、ＰＥＴ（Ａ）ともいう。）の上に、スリット状ノズルを用いて乾燥膜厚が３．０μｍ、塗布幅が１．０ｍとなるように塗布した。その後、８０℃の乾燥ゾーンを４０秒間かけて通過させ、カバーフィルムとしてポリエチレンフィルム（トレデガー社製、ＯＳＭ－Ｎ）を圧着して感光性転写材料を作製し、感光性転写材料を巻き取ってロール形態にした。 <Production of photosensitive transfer material>
In Examples 1 to 17 and Comparative Examples 1 to 5, the polymer component, the photoacid generator, the basic compound, and the surfactant were added to PGMEA so that the solid content ratio (mass ratio) shown in Table 2 below was obtained. The solution was dissolved and mixed so as to have a solid content concentration of 10% by mass and filtered through a polytetrafluoroethylene filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition.
In each Example and Comparative Example, the obtained photosensitive resin composition was used on a 30 μm-thick polyethylene terephthalate film (hereinafter also referred to as PET (A)) serving as a temporary support, using a slit nozzle. The coating was applied so that the dry film thickness was 3.0 μm and the coating width was 1.0 m. Thereafter, the film is passed through a drying zone at 80 ° C. for 40 seconds, a polyethylene film (OSM-N, manufactured by Tredegar) is pressure-bonded as a cover film to produce a photosensitive transfer material, and the photosensitive transfer material is taken up and rolled. Formed.
＜性能評価＞
　厚さ１００μｍのＰＥＴフィルム上に、銅を真空蒸着法で２００ｎｍ厚にて成膜した銅層付きＰＥＴ基板を使用した。 <Performance evaluation>
A PET substrate with a copper layer in which copper was deposited to a thickness of 200 nm on a PET film having a thickness of 100 μm by a vacuum deposition method was used.
－ラミネート適性評価－
　作製した感光性転写材料を５０ｃｍ角にカットし、カバーフィルムを剥がして、ロール温度９０℃、線圧１．０ＭＰａ、線速度４．０ｍ／ｍｉｎ．のラミネート条件で上記銅層付きＰＥＴ基板にラミネートした。中間層及び感光性樹脂層が銅層に付着している部分を目視にて判別し、中間層及び感光性樹脂層が銅層に付着している部分の仮支持体の上から油性マジックを用いてマーキングし、ＰＥＴ基板全体を撮影し、画像解析ソフト（ＩｍａｇｅＪ（米国　Ｎａｔｉｏｎａｌ　Ｉｎｓｔｉｓｕｔｅ　ｏｆ　Ｈｅａｌｔｈ製））にて、 中間層および感光性樹脂層が銅層に付着している部分と試料片全体の面積をそれぞれ算出した。そして、下記式より面積比を求め、以下の評価基準にしたがって評価した。
　面積比（％）＝中間層及び感光性樹脂層が付着した面積／試料片全体の面積×１００
　　５：９５％以上
　　４：９０％以上９５％未満
　　３：８５％以上９０％未満
　　２：８０％以上８５％未満
　　１：８０％未満 -Evaluation of suitability for lamination-
The produced photosensitive transfer material was cut into a 50 cm square, the cover film was peeled off, and the roll temperature was 90 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 4.0 m / min. It laminated on the said PET board | substrate with a copper layer on the following lamination conditions. The part where the intermediate layer and the photosensitive resin layer adhere to the copper layer is visually discriminated, and the oily magic is used from above the temporary support of the part where the intermediate layer and the photosensitive resin layer adhere to the copper layer. And image the entire PET substrate, and with image analysis software (ImageJ (manufactured by National Institute of Health, USA)), the area where the intermediate layer and the photosensitive resin layer adhere to the copper layer and the area of the entire sample piece Was calculated respectively. And area ratio was calculated | required from the following formula and evaluated according to the following evaluation criteria.
Area ratio (%) = area where the intermediate layer and the photosensitive resin layer adhere / area of the entire sample piece × 100
5: 95% or more 4: 90% or more and less than 95% 3: 85% or more and less than 90% 2: 80% or more and less than 85% 1: less than 80%
－感度評価－
　作製した感光性転写材料を巻き出した後、ラミロール温度１２０℃、線圧１．０ＭＰａ、線速度０．５ｍ／ｍｉｎ．のラミネート条件で、銅層付きＰＥＴ基板にラミネートした。仮支持体を剥離せずに線幅１０μｍのラインアンドスペースパターンマスク（Ｄｕｔｙ比　１：１）を介して超高圧水銀灯で露光後、２５℃で３時間引き置いた後に仮支持体を剥離して現像した。現像は２５℃の１．０％炭酸ナトリウム水溶液を用い、シャワー現像で３０秒行った。
　上記方法にて１０μｍのラインアンドスペースパターンを形成したとき、スペース部の残渣を走査型電子顕微鏡（ＳＥＭ）により観察し評価し、完全に残渣がなくなる露光量を求めた。上記露光量が２００ｍＪ／ｃｍ２未満であることが好ましい。
　　５：８０ｍＪ／ｃｍ２未満
　　４：８０ｍＪ／ｃｍ２以上１５０ｍＪ／ｃｍ２未満
　　３：１５０ｍＪ／ｃｍ２以上２００ｍＪ／ｃｍ２未満
　　２：２００ｍＪ／ｃｍ２以上３００ｍＪ／ｃｍ２未満
　　１：３００ｍＪ／ｃｍ２以上 -Sensitivity evaluation-
After unwinding the produced photosensitive transfer material, a lamiroll temperature of 120 ° C., a linear pressure of 1.0 MPa, and a linear velocity of 0.5 m / min. Lamination was performed on a PET substrate with a copper layer under the laminating conditions. Without peeling off the temporary support, after exposure with an ultra-high pressure mercury lamp through a line-and-space pattern mask (duty ratio 1: 1) with a line width of 10 μm, after leaving it at 25 ° C. for 3 hours, the temporary support was peeled off. Developed. Development was performed by shower development for 30 seconds using a 1.0% aqueous sodium carbonate solution at 25 ° C.
When a 10 μm line and space pattern was formed by the above method, the residue in the space was observed and evaluated with a scanning electron microscope (SEM), and the exposure amount at which the residue was completely eliminated was determined. The exposure amount is preferably less than 200 mJ / cm 2 .
5: 80mJ / cm 2 less than 4: 80mJ / cm 2 or more 150 mJ / cm 2 less than 3: 150mJ / cm 2 or more 200 mJ / cm 2 less than 2: 200mJ / cm 2 or more 300 mJ / cm 2 less than 1: 300mJ / cm 2 or more
－引き置き時間依存抑制性評価－
　作製した感光性転写材料を巻き出した後、ロール温度１２０℃、線圧１．０ＭＰａ、線速度０．５ｍ／ｍｉｎ．のラミネート条件で、銅層付きＰＥＴ基板にラミネートした。仮支持体を剥離せずに線幅１０μｍのラインアンドスペースパターンマスク（Ｄｕｔｙ比　１：１）を介して、上記感度評価にて残渣がなくなった露光量により露光後、２５℃で１２時間引き置いた後に仮支持体を剥離して現像した。現像は２５℃の１．０％炭酸ナトリウム水溶液を用い、シャワー現像で３０秒行った。
　得られたラインアンドスペースパターンの線幅を走査型電子顕微鏡（ＳＥＭ）により観察し、１０μｍからの線幅の変動を評価した。１０μｍからの線幅の変動が１．５μｍ未満であることが好ましい。
　　５：０．５μｍ未満
　　４：０．５μｍ以上１．０μｍ未満
　　３：１．０μｍ以上１．５μｍ未満
　　２：１．５μｍ以上３μｍ未満
　　１：３μｍ以上 -Evaluation of restraint time dependence inhibition
After unwinding the produced photosensitive transfer material, the roll temperature was 120 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 0.5 m / min. Lamination was performed on a PET substrate with a copper layer under the laminating conditions. Without exposing the temporary support, it was left at 25 ° C. for 12 hours after exposure with the exposure amount with no residue in the sensitivity evaluation through a line and space pattern mask (Duty ratio 1: 1) having a line width of 10 μm. Thereafter, the temporary support was peeled off and developed. Development was performed by shower development for 30 seconds using a 1.0% aqueous sodium carbonate solution at 25 ° C.
The line width of the obtained line and space pattern was observed with a scanning electron microscope (SEM), and the fluctuation of the line width from 10 μm was evaluated. The line width variation from 10 μm is preferably less than 1.5 μm.
5: Less than 0.5 μm 4: 0.5 μm or more and less than 1.0 μm 3: 1.0 μm or more and less than 1.5 μm 2: 1.5 μm or more and less than 3 μm 1: 3 μm or more
－解像性評価－
　作製した感光性転写材料を、ロール温度１２０℃、線圧０．８ＭＰａ、線速度１．０ｍ／ｍｉｎ．のラミネート条件で銅層付きＰＥＴ基板にラミネートした。
　仮支持体を剥離せずに、線幅３μｍ～２０μｍのラインアンドスペースパターンマスク（Ｄｕｔｙ比　１：１）を介して超高圧水銀灯で露光後、３時間引き置いた後に仮支持体を剥離して現像した。現像は２５℃の１．０％炭酸ナトリウム水溶液を用い、シャワー現像で３０秒行った。次いで２５℃の銅エッチング液（関東化学（株）製Ｃｕ－０２）を用いて銅層をディップ法にて６０秒間エッチングした。残った感光性樹脂層を５０℃の剥離液（関東化学（株）製ＫＰ－３０１）を用い、シャワーで剥離することで、ラインアンドスペースが１０μｍの導電パターンを有する銅配線を形成した。銅配線のＬＷＲ（Ｌｉｎｅ　Ｗｉｄｔｈ　Ｒｏｕｇｈｎｅｓｓ、銅配線の線幅を２５０点計測した値の３σ）を求め、下記基準を指標にして直線性を評価した。３以上が実用可能レベルである。
　　５：ＬＷＲが２００ｎｍ以下である。
　　４：ＬＷＲが２３０ｎｍ以下かつ２００ｎｍを超える値である。
　　３：ＬＷＲが２５０ｎｍ以下かつ２３０ｎｍを超える値である。
　　２：ＬＷＲが３００ｎｍ以下かつ２５０ｎｍを超える値である。
　　１：ＬＷＲが３００ｎｍより大きい、又は導電パターンが形成できなかった。 -Resolution evaluation-
The produced photosensitive transfer material was subjected to a roll temperature of 120 ° C., a linear pressure of 0.8 MPa, and a linear velocity of 1.0 m / min. It laminated on the PET board | substrate with a copper layer on the lamination conditions of these.
Without peeling off the temporary support, it was exposed with an ultra-high pressure mercury lamp through a line-and-space pattern mask (duty ratio 1: 1) with a line width of 3 μm to 20 μm, and after leaving for 3 hours, the temporary support was peeled off. Developed. Development was performed by shower development for 30 seconds using a 1.0% aqueous sodium carbonate solution at 25 ° C. Next, the copper layer was etched by a dipping method for 60 seconds using a copper etching solution at 25 ° C. (Cu-02 manufactured by Kanto Chemical Co., Inc.). The remaining photosensitive resin layer was peeled off with a shower using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.) at 50 ° C. to form a copper wiring having a conductive pattern with a line and space of 10 μm. The copper wiring LWR (Line Width Roughness, 3σ of a value obtained by measuring the width of the copper wiring at 250 points) was obtained, and the linearity was evaluated using the following criteria as an index. Three or more are practical levels.
5: LWR is 200 nm or less.
4: LWR is 230 nm or less and more than 200 nm.
3: LWR is a value of 250 nm or less and exceeding 230 nm.
2: LWR is a value of 300 nm or less and exceeding 250 nm.
1: LWR was larger than 300 nm or a conductive pattern could not be formed.
　各実施例及び各比較例における評価結果を、まとめて表２に示す。 Table 2 summarizes the evaluation results in each example and each comparative example.
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
　上記表２より、実施例１～１７の感光性転写材料は、比較例１～５の感光性転写材料と比べ、ラミネート適性、及び、解像性に優れることがわかる。
　また、上記表２より、実施例１～１７の感光性転写材料は、感度、及び、引き置き時間依存抑制性にも優れる。 From Table 2 above, it can be seen that the photosensitive transfer materials of Examples 1 to 17 are superior in laminate suitability and resolution as compared with the photosensitive transfer materials of Comparative Examples 1 to 5.
Further, from the above Table 2, the photosensitive transfer materials of Examples 1 to 17 are excellent in sensitivity and retention time dependence suppression.
（実施例１０１）
　１００μｍ厚ＰＥＴ基材上に、第２層の導電層としてＩＴＯをスパッタリングで１５０ｎｍ厚にて成膜し、その上に第１層の導電層として銅を真空蒸着法で２００ｎｍ厚にて成膜して、回路形成用基板とした。
　銅層上に実施例１で得た感光性転写材料をラミネートした（ラミロール温度１２０℃、線圧０．８ＭＰａ、線速度１．０ｍ／ｍｉｎ．）。ラミネートした支持体を仮支持体を剥離せずに一方向に導電層パッドが連結された構成を持つ図２に示すパターン（以下、「パターンＡ」とも称する。）を設けたフォトマスクを用いてコンタクトパターン露光した。
　なお、図２に示すパターンＡは、実線部ＳＬ及びグレー部Ｇが遮光部であり、点線部ＤＬはアライメント合わせの枠を仮想的に示したものである。
　その後仮支持体を剥離し、現像、水洗を行ってパターンＡを得た。次いで銅エッチング液（関東化学（株）製Ｃｕ－０２）を用いて銅層をエッチングした後、ＩＴＯエッチング液（関東化学（株）製ＩＴＯ－０２）を用いてＩＴＯ層をエッチングすることで、銅とＩＴＯが共にパターンＡで描画された基板を得た。
　次いで、アライメントを合わせた状態で図３に示すパターン（以下、「パターンＢ」とも称する。）の開口部を設けたフォトマスクを用いてパターン露光し、現像、水洗を行った。
　なお、図３に示すパターンＢは、グレー部Ｇが遮光部であり、点線部ＤＬはアライメント合わせの枠を仮想的に示したものである。
　その後、Ｃｕ－０２を用いて銅層をエッチングし、残った感光性樹脂層を剥離液（関東化学（株）製ＫＰ－３０１）を用いて剥離し、回路配線基板を得た。
　得られた回路配線基板を、顕微鏡で観察したところ、剥がれや欠けなどは無く、きれいなパターンであった。 (Example 101)
On the 100 μm-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer at a thickness of 200 nm by vacuum evaporation. Thus, a circuit forming substrate was obtained.
The photosensitive transfer material obtained in Example 1 was laminated on the copper layer (Lamiroll temperature 120 ° C., linear pressure 0.8 MPa, linear velocity 1.0 m / min.). A photomask provided with a pattern (hereinafter also referred to as “pattern A”) shown in FIG. 2 having a structure in which conductive layer pads are connected in one direction without peeling off the temporary support from the laminated support is used. The contact pattern was exposed.
In the pattern A shown in FIG. 2, the solid line portion SL and the gray portion G are light shielding portions, and the dotted line portion DL virtually shows an alignment alignment frame.
Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A. Next, after etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), 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.
Next, pattern alignment was performed using a photomask provided with openings of a pattern shown in FIG. 3 (hereinafter also referred to as “pattern B”) in the aligned state, and development and washing were performed.
In the pattern B shown in FIG. 3, the gray portion G is a light shielding portion, and the dotted line portion DL is a virtual alignment alignment frame.
Thereafter, the copper layer was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
When the obtained circuit wiring board was observed with a microscope, it was a clean pattern with no peeling or chipping.
（実施例１０２）
　１００μｍ厚ＰＥＴ基材上に、第２層の導電層としてＩＴＯをスパッタリングで１５０ｎｍ厚にて成膜し、その上に第１層の導電層として銅を真空蒸着法で２００ｎｍ厚にて成膜して、回路形成基板とした。
　銅層上に実施例１で得た感光性転写材料を巻き出してラミネートした（ロール温度１２０℃、線圧０．８ＭＰａ、線速度１．０ｍ／ｍｉｎ．）。ラミネートした支持体を仮支持体を剥離せずに一方向に導電層パッドが連結された構成を持つパターンＡを設けたフォトマスクを用いてパターン露光した。その後仮支持体を剥離し、現像、水洗を行ってパターンＡを得た。次いで銅エッチング液（関東化学（株）製Ｃｕ－０２）を用いて銅層をエッチングした後、ＩＴＯエッチング液（関東化学（株）製ＩＴＯ－０２）を用いてＩＴＯ層をエッチングすることで、銅とＩＴＯが共にパターンＡで描画された基板を得た。
　次いで、残存しているレジスト上に保護層としてＰＥＴ（Ａ）をラミネートした。この状態で、アライメントを合わせた状態でパターンＢの開口部を設けたフォトマスクを用いてパターン露光し、ＰＥＴ（Ａ）を剥離した後に現像、水洗を行った。その後、Ｃｕ－０２を用いて銅配線をエッチングし、残った感光性樹脂層を剥離液（関東化学（株）製ＫＰ－３０１）を用いて剥離し、回路配線基板を得た。
　得られた回路配線基板を、顕微鏡で観察したところ、剥がれや欠けなどは無く、きれいなパターンであった。 (Example 102)
On the 100 μm-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer at a thickness of 200 nm by vacuum evaporation. Thus, a circuit forming substrate was obtained.
The photosensitive transfer material obtained in Example 1 was unwound and laminated on the copper layer (roll temperature 120 ° C., linear pressure 0.8 MPa, linear velocity 1.0 m / min.). The laminated support was subjected to pattern exposure using a photomask provided with a pattern A having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A. Next, after etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), 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.
Next, PET (A) was laminated as a protective layer on the remaining resist. In this state, pattern exposure was performed using a photomask provided with an opening of pattern B in the aligned state, and after developing PET (A), development and washing were performed. Thereafter, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was stripped using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
When the obtained circuit wiring board was observed with a microscope, it was a clean pattern with no peeling or chipping.
（実施例１０３）
　１００μｍ厚シクロオレフィンポリマー（ＣＯＰ）基材上に、第２層の導電層としてＩＴＯをスパッタリングで１５０ｎｍ厚にて成膜し、その上に第１層の導電層として銅を真空蒸着法で２００ｎｍ厚にて成膜して、導電パターン形成用の基板とした。
　銅層上に実施例１で得た感光性転写材料を基板に貼り合わせて（ロール温度１００℃、線圧０．８ＭＰａ、線速度３．０ｍ／ｍｉｎ．）、積層体とした。積層体を、仮支持体を剥離せずに一方向に導電層パッドが連結された構成を持つパターンＡを設けたフォトマスクを用いてパターン露光した。その後仮支持体を剥離し、現像、水洗を行ってパターンＡで描画された樹脂パターンを得た。次いで銅エッチング液（関東化学（株）製Ｃｕ－０２）を用いて銅層をエッチングした後、ＩＴＯエッチング液（関東化学（株）製ＩＴＯ－０２）を用いてＩＴＯ層をエッチングし、剥離液（関東化学（株）製ＫＰ－３０１）を用いて剥離することで、銅とＩＴＯが共にパターンＡで描画された基板を得た。
　次いで、残存しているレジスト上に、実施例１で得られた感光性転写材料を貼り合わせた（ロール温度１００℃、線圧０．８ＭＰａ、線速度３．０ｍ／ｍｉｎ．）。この状態で、アライメントを合わせた状態でパターンＢの開口部を設けたフォトマスクを用いてパターン露光し、感光性転写材料の仮支持体を剥離した後に現像、水洗を行った。その後、Ｃｕ－０２を用いて銅配線をエッチングし、残った感光性樹脂層を剥離液（関東化学（株）製ＫＰ－３０１）を用いて剥離し、導電パターンを有する回路配線基板を得た。
　得られた回路配線基板を、顕微鏡で観察したところ、剥がれ、欠けなどは無く、きれいなパターンであった。 (Example 103)
On the 100 μm-thick cycloolefin polymer (COP) substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer by a thickness of 200 nm by vacuum evaporation. To form a substrate for forming a conductive pattern.
The photosensitive transfer material obtained in Example 1 was bonded to a substrate on a copper layer (roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.) To obtain a laminate. The laminate was subjected to pattern exposure using a photomask provided with a pattern A having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a resin pattern drawn with pattern A. Next, after etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), and a peeling solution. By peeling using (KP-301, manufactured by Kanto Chemical Co., Inc.), a substrate on which both copper and ITO were drawn with the pattern A was obtained.
Next, the photosensitive transfer material obtained in Example 1 was bonded onto the remaining resist (roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.). In this state, pattern exposure was performed using a photomask provided with openings of pattern B in the aligned state, and the temporary support of the photosensitive transfer material was peeled off, followed by development and washing with water. Thereafter, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board having a conductive pattern. .
When the obtained circuit wiring board was observed with a microscope, it was a clean pattern with no peeling or chipping.
　２０１８年５月２２日に出願された日本国特許出願第２０１８－０９８３３１号の開示は、その全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、及び、技術規格は、個々の文献、特許出願、及び、技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The disclosure of Japanese Patent Application No. 2018-098331 filed on May 22, 2018 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described in this specification are the same as if each document, patent application, and technical standard were specifically and individually stated to be incorporated by reference. Which is incorporated herein by reference.
　１０：仮支持体、１２：感光性樹脂層、１４：カバーフィルム、１００：感光性転写材料、ＳＬ：実線部、Ｇ：グレー部、ＤＬ：点線部
  10: Temporary support, 12: Photosensitive resin layer, 14: Cover film, 100: Photosensitive transfer material, SL: Solid line part, G: Gray part, DL: Dotted line part

Claims (11)

  1. 　仮支持体と、
    　感光性樹脂層とを有し、
    　前記感光性樹脂層が、下記ａ１及びａ２の少なくとも一方を満たす重合体成分、並びに、光酸発生剤を含み、
    　前記重合体成分のガラス転移温度が、９０℃以下である
    　感光性転写材料。
    　ａ１：酸分解性基で保護された酸基を有する構成単位、及び、ｐＫａＨが３以上の基を有する構成単位を有する重合体を含む重合体成分
    　ａ２：酸分解性基で保護された酸基を有する構成単位を有する重合体、及び、ｐＫａＨが３以上の基を有する構成単位を有する重合体を含む重合体成分     A temporary support;
    A photosensitive resin layer,
    The photosensitive resin layer contains a polymer component that satisfies at least one of the following a1 and a2, and a photoacid generator,
    The photosensitive transfer material whose glass transition temperature of the said polymer component is 90 degrees C or less.
    a1: Polymer component containing a structural unit having an acid group protected by an acid-decomposable group and a polymer having a structural unit having a pKaH group of 3 or more a2: An acid group protected by an acid-decomposable group And a polymer component comprising a polymer having a structural unit having a structural unit having a pKaH group of 3 or more
  2. 　前記感光性樹脂層中に含まれる全てのｐＫａＨが３以上の基のうち、前記重合体成分に含まれるｐＫａＨが３以上の基の割合が、３０モル％以上である請求項１に記載の感光性転写材料。 2. The photosensitive composition according to claim 1, wherein among all the groups having 3 or more pKaH contained in the photosensitive resin layer, the proportion of the group having 3 or more pKaH contained in the polymer component is 30 mol% or more. Transfer material.
  3. 　前記感光性樹脂層中に含まれる全てのｐＫａＨが３以上の基のうち、前記重合体成分に含まれるｐＫａＨが３以上の基の割合が、５０モル％以上である請求項１又は請求項２に記載の感光性転写材料。 The ratio of the group having 3 or more pKaH contained in the polymer component among all the groups having 3 or more pKaH contained in the photosensitive resin layer is 50 mol% or more. The photosensitive transfer material described in 1.
  4. 　前記重合体成分における重合体が、酸分解性基で保護された酸基を有する構成単位及びｐＫａＨが３以上の基を有する構成単位以外の構成単位を更に有する請求項１～請求項３のいずれか１項に記載の感光性転写材料。 The polymer in the polymer component further has a structural unit other than a structural unit having an acid group protected with an acid-decomposable group and a structural unit having a pKaH group of 3 or more. 2. The photosensitive transfer material according to item 1.
  5. 　前記ｐＫａＨが３以上の基を有する構成単位が、下記式Ｉ又は式ＩＩで表される構成単位である請求項１～請求項４のいずれか１項に記載の感光性転写材料。
    Figure JPOXMLDOC01-appb-C000001
    　式Ｉ及び式ＩＩ中、Ｒ１は水素原子又はメチル基を表し、Ｚは単結合、メチレン基、アリーレン基、－Ｏ－、－Ｃ（＝Ｏ）－ＮＨ－又は－Ｃ（＝Ｏ）－Ｏ－を表し、Ｒ２は単結合、又は、エーテル結合、ウレタン結合、ウレア結合、アミド結合、エステル結合及びカーボネート結合よりなる群から選ばれた少なくとも１種の基を有していてもよい炭素数１～１０の直鎖状、分岐状若しくは環状のアルキレン基を表し、Ｒ３及びＲ４はそれぞれ独立に、水素原子、又は、エーテル結合、チオエーテル結合、ヒドロキシ基、ホルミル基、アセトキシ基、シアノ基、ウレタン結合、ウレア結合、アミド結合、エステル結合、カーボネート結合及び芳香族基よりなる群から選ばれた少なくとも１種の基を有していてもよい炭素数１～２０の直鎖状、分岐状若しくは環状のアルキル基を表し、Ｒ２とＲ３、Ｒ２とＲ４、又は、Ｒ３とＲ４はそれぞれ結合して環を形成していてもよく、Ｑ１は、窒素原子を有する芳香族基又は含窒素複素芳香族基を表す。     The photosensitive transfer material according to any one of claims 1 to 4, wherein the structural unit having a pKaH group of 3 or more is a structural unit represented by the following formula I or formula II.
    Figure JPOXMLDOC01-appb-C000001
    In Formulas I and II, R 1 represents a hydrogen atom or a methyl group, and Z is a single bond, a methylene group, an arylene group, —O—, —C (═O) —NH—, or —C (═O) —. Represents O—, and R 2 may have a single bond or at least one group selected from the group consisting of an ether bond, a urethane bond, a urea bond, an amide bond, an ester bond and a carbonate bond. Represents a linear, branched or cyclic alkylene group of 1 to 10, wherein R 3 and R 4 are each independently a hydrogen atom, or an ether bond, a thioether bond, a hydroxy group, a formyl group, an acetoxy group, a cyano group A linear group having 1 to 20 carbon atoms which may have at least one group selected from the group consisting of a group, a urethane bond, a urea bond, an amide bond, an ester bond, a carbonate bond and an aromatic group, Represents a branched or cyclic alkyl group, R 2 and R 3 , R 2 and R 4 , or R 3 and R 4 may be bonded to each other to form a ring, and Q 1 represents a nitrogen atom Represents an aromatic group or a nitrogen-containing heteroaromatic group.
  6. 　前記ｐＫａＨが３以上の基を有する構成単位が、前記式Ｉで表される構成単位である請求項５に記載の感光性転写材料。 6. The photosensitive transfer material according to claim 5, wherein the structural unit in which the pKaH has a group of 3 or more is a structural unit represented by the formula I.
  7. 　前記酸分解性基で保護された酸基を有する構成単位が、下記式Ａで表される構成単位である請求項１～請求項６のいずれか１項に記載の感光性転写材料。
    Figure JPOXMLDOC01-appb-C000002
    　式Ａ中、Ｒ３１及びＲ３２はそれぞれ独立に、水素原子、アルキル基又はアリール基を表し、少なくともＲ３１及びＲ３２のいずれか一方がアルキル基又はアリール基であり、Ｒ３３はアルキル基又はアリール基を表し、Ｒ３１又はＲ３２と、Ｒ３３とが連結して環状エーテルを形成してもよく、Ｒ３４は水素原子又はメチル基を表し、Ｘ０は単結合又は２価の連結基を表す。     7. The photosensitive transfer material according to claim 1, wherein the structural unit having an acid group protected by an acid-decomposable group is a structural unit represented by the following formula A.
    Figure JPOXMLDOC01-appb-C000002
    In formula A, R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group or Represents an aryl group, R 31 or R 32 and R 33 may combine to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or a divalent linking group. Represents.
  8. 　請求項１～請求項７のいずれか１項に記載の感光性転写材料における前記感光性樹脂層を基板に接触させて貼り合わせる工程と、
    　前記感光性樹脂層をパターン露光する工程と、
    　露光された前記感光性樹脂層を現像してパターンを形成する工程と、をこの順に含む
    　樹脂パターンの製造方法。     A step of bringing the photosensitive resin layer in the photosensitive transfer material according to any one of claims 1 to 7 into contact with a substrate and bonding the substrate;
    Pattern exposing the photosensitive resin layer;
    And developing the exposed photosensitive resin layer to form a pattern, in this order.
  9. 　請求項１～請求項７のいずれか１項に記載の感光性転写材料の前記感光性樹脂層を、導電層を有する基板に接触させて貼り合わせる工程と、
    　前記感光性樹脂層をパターン露光する工程と、
    　露光された前記感光性樹脂層を現像してパターンを形成する工程と、
    　前記パターンが配置されていない領域における導電層をエッチング処理する工程と、をこの順に含む
    　回路配線の製造方法。     A step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of claims 1 to 7 into contact with a substrate having a conductive layer;
    Pattern exposing the photosensitive resin layer;
    Developing the exposed photosensitive resin layer to form a pattern; and
    And a step of etching the conductive layer in a region where the pattern is not disposed, in this order.
  10. 　前記導電層が、銅を含む層である請求項９に記載の回路配線の製造方法。 The circuit wiring manufacturing method according to claim 9, wherein the conductive layer is a layer containing copper.
  11. 　請求項１～請求項７のいずれか１項に記載の感光性転写材料の前記感光性樹脂層を、導電層を有する基板に接触させて貼り合わせる工程と、
    　前記感光性樹脂層をパターン露光する工程と、
    　露光された前記感光性樹脂層を現像してパターンを形成する工程と、
    前記パターンが配置されていない領域における導電層をエッチング処理する工程と、をこの順に含む
    　タッチパネルの製造方法。     A step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of claims 1 to 7 into contact with a substrate having a conductive layer;
    Pattern exposing the photosensitive resin layer;
    Developing the exposed photosensitive resin layer to form a pattern;
    And a step of etching the conductive layer in a region where the pattern is not disposed, in this order.
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