WO2020040054A1 - Transfer film, laminate, and pattern forming method - Google Patents

Transfer film, laminate, and pattern forming method Download PDF

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Publication number
WO2020040054A1
WO2020040054A1 PCT/JP2019/032150 JP2019032150W WO2020040054A1 WO 2020040054 A1 WO2020040054 A1 WO 2020040054A1 JP 2019032150 W JP2019032150 W JP 2019032150W WO 2020040054 A1 WO2020040054 A1 WO 2020040054A1
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WIPO (PCT)
Prior art keywords
light
mass
photosensitive layer
transfer film
shielding layer
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PCT/JP2019/032150
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French (fr)
Japanese (ja)
Inventor
達也 霜山
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to CN201980042030.XA priority Critical patent/CN112352199A/en
Priority to JP2020538358A priority patent/JP7094372B2/en
Publication of WO2020040054A1 publication Critical patent/WO2020040054A1/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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the present disclosure relates to a transfer film, a laminate, and a pattern forming method.
  • a tablet-type input device is arranged on a surface of a liquid crystal device or the like.
  • a device that can input information corresponding to an instruction image by touching a position where the instruction image is displayed with a finger or a touch pen while referring to an instruction image displayed in an image display area of a liquid crystal device.
  • the input device hereinafter, also referred to as a touch panel
  • the input device include a resistive film type and a capacitance type.
  • a capacitance-type input device there is an advantage that a light-transmitting conductive film may be simply formed on one substrate.
  • a wiring board in which metal wiring is provided on a substrate is formed by forming a patterned resist film by a photoresist method on a metal film formed on the substrate and etching the metal film using the resist film as a mask. Can be made.
  • an operation of etching using a patterned resist film as a mask is performed on both sides of the board.
  • ⁇ As a technique related to the above, there is a disclosure related to a method of patterning both surfaces of a transparent substrate (for example, see Japanese Patent Application Laid-Open No. 2011-154080). Specifically, in forming the pattern of the transparent metal film provided on both the front and back surfaces of the transparent substrate, an opaque layer that blocks exposure light is formed on at least one of the transparent metal films, It is described that a photoresist film is formed by applying a photoresist on both front and back surfaces, and different pattern exposures can be performed on both surfaces having the photoresist film to form respective resist patterns.
  • a first photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator, and a light having a relatively higher light sensitivity than the first photosensitive layer on a support, a first photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator, and a light having a relatively higher light sensitivity than the first photosensitive layer.
  • a photosensitive transfer sheet in which a second photosensitive layer exhibiting sensitivity is laminated in this order is disclosed (for example, see JP-A-2005-331695).
  • an opaque layer is provided to prevent light irradiated on one side from transmitting to the other side.
  • metal such as aluminum
  • the number of steps increases.
  • the opaque layer is not removed during the development of the photoresist, it is impossible to simultaneously etch both sides of the transparent substrate as it is after development.
  • light at the time of pattern exposure is easily reflected by the opaque layer.
  • the present disclosure has been made in view of the above.
  • the problem to be solved by one embodiment of the present invention is that during pattern exposure after transfer, the influence on pattern formability on the other side due to irradiation light from one side of the transparent substrate is suppressed.
  • An object of the present invention is to provide a transfer film or a laminate that can easily form a fine pattern.
  • the problem to be solved by another embodiment of the present invention is to suppress the influence on the pattern formability on the other side due to irradiation light from one side of the transparent substrate during pattern exposure after transfer.
  • Another object of the present invention is to provide a pattern forming method capable of easily forming a fine pattern.
  • a temporary support a first photosensitive layer containing a binder polymer, a polymerizable compound, and a photopolymerization initiator, and a light-shielding layer containing at least a binder polymer and having an optical density of 0.5 or more. It is a transfer film having this order.
  • the ultraviolet absorbing material contains carbon black.
  • ⁇ 4> The transfer film according to any one of ⁇ 1> to ⁇ 3>, wherein the light-shielding layer further contains a polymerizable compound.
  • ⁇ 5> The transfer film according to any one of ⁇ 1> to ⁇ 4>, wherein the content of the photopolymerization initiator is 1% by mass or less based on the total solid content of the light-shielding layer.
  • ⁇ 6> The transfer film according to any one of ⁇ 1> to ⁇ 5>, including an intermediate layer between the first photosensitive layer and the light-shielding layer.
  • ⁇ 7> The transfer film according to ⁇ 6>, wherein the intermediate layer contains a binder polymer having solubility in water or a lower alcohol having 1 to 4 carbon atoms.
  • ⁇ 8> The transfer film according to ⁇ 6> or ⁇ 7>, wherein the intermediate layer further contains a polymerizable compound and a photopolymerization initiator.
  • ⁇ 9> A laminate including a transparent base material and the transfer film according to any one of ⁇ 1> to ⁇ 8>.
  • ⁇ 10> The laminate according to ⁇ 9>, wherein the transparent substrate has a second photosensitive layer on a side opposite to a side on which the transfer film is laminated.
  • the second photosensitive layer contains a binder polymer, a polymerizable compound, and a photopolymerization initiator.
  • ⁇ 12> a step of attaching the transfer film according to any one of ⁇ 1> to ⁇ 8> to one side of the transparent substrate, and a binder polymer and a polymerizable compound on the other side of the transparent substrate. Forming a second photosensitive layer containing a photoinitiator, and irradiating both sides of the transparent substrate with light in different patterns, respectively. Forming different patterns on both sides of the transparent substrate by developing both sides of the material.
  • ⁇ 13> The pattern forming method according to ⁇ 12>, wherein the transparent substrate has at least one of a metal electrode and a metal wiring on both surfaces.
  • ⁇ 14> The pattern forming method according to ⁇ 12> or ⁇ 13>, which is used for forming at least one of a touch panel electrode and a touch panel wiring.
  • the influence on the pattern formability on the other side due to the irradiation light from one side of the transparent substrate is suppressed, and the fine pattern is easily formed.
  • a transfer film or laminate capable of forming a pattern is provided.
  • at the time of pattern exposure after transfer while suppressing the effect on the pattern formability of the other side due to irradiation light from one side of the transparent substrate, easily A pattern forming method capable of forming a fine pattern is provided.
  • FIG. 1 is a cross-sectional configuration diagram illustrating an embodiment of the transfer film of the present disclosure.
  • FIG. 2 is a cross-sectional configuration diagram illustrating an embodiment of the laminate of the present disclosure.
  • FIG. 3 is a cross-sectional configuration diagram illustrating another embodiment of the laminate of the present disclosure.
  • FIG. 4 is a process diagram for explaining that different patterns are simultaneously formed on both sides of a transparent substrate by the pattern forming method of the present disclosure.
  • “to” indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit and the upper limit.
  • the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described in stages.
  • the upper limit or the lower limit of the numerical range may be replaced with the value shown in the embodiment.
  • the notation of not indicating substituted or unsubstituted includes not only one having no substituent but also one 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).
  • “mass%” and “weight%” have the same meaning, and “mass part” and “part by weight” have the same meaning.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the amount of each component in the composition when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, means the total amount of the plurality of substances present in the composition I do.
  • step is included in this term as long as the intended purpose of the step is achieved not only in an independent step but also in cases where it cannot be clearly distinguished from other steps.
  • (meth) acrylic acid is a concept including both acrylic acid and methacrylic acid
  • (meth) acrylate is a concept including both acrylate and methacrylate
  • (meth) acrylate” is a concept encompassing both acryloyl and methacryloyl groups.
  • the ratio of a structural unit in a resin represents a mass ratio unless otherwise specified.
  • the molecular weight when there is a molecular weight distribution represents a weight average molecular weight (Mw), unless otherwise specified.
  • the transfer film of the present disclosure includes a temporary support, a first photosensitive layer containing a binder polymer, a polymerizable compound, and a photopolymerization initiator, and a light-shielding film containing at least a binder polymer and having an optical density of 0.5 or more. And in this order, and if necessary, may further have another layer such as an intermediate layer.
  • an opaque layer is provided between layers to form a layer structure in which light irradiated on one side of a transparent base material is not transmitted to the other side.
  • the light irradiated on one side of the transparent substrate is prevented from being transmitted, and the photosensitive state (latent image) on the other side is hardly disturbed.
  • a metal such as aluminum is used for the opaque layer. Therefore, when a wiring pattern is formed by etching using a resist pattern as a mask, an etching step for the opaque layer must be provided in advance in addition to an etching step for forming the wiring pattern.
  • the opaque layer disposed between the layers is a metal layer as in the invention described in Japanese Patent Application Laid-Open No. 2011-154080
  • the metal layer involves reflection of light to some extent. Reflection from the opaque layer produces an unwanted exposure effect, which results in a loss of pattern definition.
  • the opaque layer cannot be developed and removed at the same time as the photoresist by the developing treatment after light irradiation, the opaque layer remains as it is at the time of development of the photoresist film formed on both sides of the transparent substrate, for example. Therefore, a state that can be etched simultaneously with the development cannot be formed.
  • the first photosensitive layer containing the binder polymer, the polymerizable compound, and the photopolymerization initiator, the binder polymer, and the optical density are 0.5 on the temporary support.
  • the light shielding layer described above is laminated in this order to form a laminated structure.
  • the transfer film 41 is attached to one side of the transparent substrate 21 to have a laminated structure of the transparent substrate 21 / the light shielding layer 13 / the first photosensitive layer 17 / the temporary support 19.
  • the irradiation light irradiated from one side is blocked by the light shielding layer 13 and the other side (for example, the side of the transparent substrate 21 of the laminate) ) Is suppressed, and light from the other side is similarly blocked by the light shielding layer 13, so that transmission to one side is suppressed.
  • the first photosensitive layer 17 and the light-shielding layer 13 are formed not only in the first photosensitive layer 17 but also in a region other than the region where the first photosensitive layer 17 is exposed by the irradiation light from one side.
  • the light-shielding layer 13 is also favorably developed and removed, so that a state in which etching can be performed simultaneously with development is obtained, and the light-shielding layer 13 hardly remains on the transparent substrate 21. As a result, a highly accurate pattern is formed on the transparent substrate 21. This is because, for example, as shown in FIG. 3, a transfer film 41 is bonded to one side of the transparent substrate 21 and another transfer film 43 having the second photosensitive layer 27 is bonded to the other side. This is more remarkable when the laminated body 101 has a laminated structure of the temporary support 19 / first photosensitive layer 17 / light shielding layer 13 / transparent substrate 21 / second photosensitive layer 27 / temporary support 19a.
  • the irradiation light irradiated from one side is blocked by the light blocking layer 13 and the other side (for example, the temporary support 19a side of the laminate in FIG. 3).
  • the transmission to the one side is also blocked by the light-shielding layer 13 so that the irradiation light irradiated from the other side is also blocked. Be suppressed.
  • the first photosensitive layer and the light-shielding layer are good in not only the first photosensitive layer 17 but also the light-shielding layer 13 in a region where the first photosensitive layer is not exposed to light from one side.
  • the light-shielding layer 13 and the second photosensitive layer do not easily remain on the transparent substrate 21, a highly accurate pattern with few residues is formed on the transparent substrate 21.
  • the light-shielding layer disposed between the layers easily absorbs irradiation light and hardly reflects the irradiation light, so that unnecessary exposure effects due to the reflected light are suppressed. This increases the definition of the pattern.
  • the light-shielding layer according to the present disclosure is a layer that can be removed during the development of the first photosensitive layer, it can be removed in the course of development that reveals the pattern, and can be etched. Therefore, both sides can be etched as they are after development.
  • the first photosensitive layer is a photosensitive negative type layer disposed on a temporary support, and includes at least a binder polymer, a polymerizable compound, and a photopolymerization initiator.
  • the first photosensitive layer may further contain other components such as a surfactant, a solvent, and an additive, if necessary.
  • the first photosensitive layer contains at least one binder polymer.
  • the binder polymer is preferably a resin that can be dissolved by contact with an alkaline solvent (so-called alkali-soluble resin).
  • the acid value of the binder polymer is not particularly limited, but is preferably 60 mg / KOH or more from the viewpoint of developability.
  • the binder polymer is preferably a binder polymer having an acid value of 60 mg KOH / g or more, more preferably an alkali-soluble resin having an acid value of 60 mg KOH / g or more, and containing a carboxy group having an acid value of 60 mg KOH / g or more.
  • An acrylic resin is particularly preferred.
  • the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more (hereinafter, may be referred to as a specific polymer) is not particularly limited as long as it satisfies the above acid value conditions, and may be appropriately selected from known resins. Can be used.
  • a binder polymer which is a carboxy group-containing acrylic resin having an acid value of 60 mg KOH / g or more, described in paragraphs 0033 to 0052 of JP-A-2010-237589 are examples of the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589.
  • a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used as the specific polymer in the present embodiment.
  • the (meth) acrylic resin refers to a resin containing at least one of a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylate.
  • the total ratio of the structural units derived from (meth) acrylic acid and the structural units derived from (meth) acrylic acid ester in the (meth) acrylic resin is preferably at least 30 mol%, more preferably at least 50 mol%.
  • the preferred range of the copolymerization ratio of the monomer having a carboxy group in the specific polymer is 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, with respect to 100% by mass of the specific polymer. More preferably, it is in the range of 10% by mass to 20% by mass.
  • the specific polymer may have a reactive group. Means for introducing a reactive group into the specific polymer include a hydroxyl group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, a sulfonic acid, an epoxy compound, a blocked isocyanate, an isocyanate, and a vinyl sulfone.
  • a method of reacting a compound, an aldehyde compound, a methylol compound, a carboxylic anhydride, or the like can be used.
  • the reactive group is preferably a radical polymerizable group, more preferably an ethylenically unsaturated group, and particularly preferably a (meth) acryloxy group.
  • the binder polymer may have a structural unit having an aromatic ring from the viewpoint of moisture permeability and strength after curing.
  • the monomer forming the structural unit having an aromatic ring include styrene, tert-butoxystyrene, 4-methylstyrene, ⁇ -methylstyrene, benzyl (meth) acrylate, and the like.
  • the constituent unit having an aromatic ring is preferably a constituent unit derived from styrene.
  • the content of the constituent unit having an aromatic ring is preferably from 5% by mass to 90% by mass, and more preferably from 10% by mass to 90% by mass, based on the total mass of the binder polymer.
  • the content is more preferably 70% by mass, and even more preferably 20% by mass to 50% by mass.
  • the binder polymer particularly the specific polymer, preferably has a structural unit having an aliphatic cyclic skeleton from the viewpoint of tackiness and strength after curing.
  • Specific examples of the monomer forming the structural unit having an aliphatic cyclic skeleton include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
  • a dicyclopentane ring, a cyclohexane ring, an isoboron ring, a tricyclodecane ring and the like are preferably exemplified. Among them, a tricyclodecane ring is particularly preferred.
  • the content of the constituent unit having an alicyclic skeleton may be 5% by mass to 90% by mass based on the total mass of the binder polymer. It is more preferably from 10% by mass to 80% by mass, and still more preferably from 20% by mass to 70% by mass.
  • the binder polymer particularly the specific polymer, preferably has a structural unit having an ethylenically unsaturated group from the viewpoint of tackiness and strength after curing.
  • a (meth) acryl group is preferable, and a (meth) acryloxy group is more preferable.
  • the binder polymer contains a constituent unit having an ethylenically unsaturated group
  • the content of the constituent unit having an ethylenically unsaturated group may be 5% by mass to 70% by mass based on the total mass of the binder polymer. It is more preferably from 10% by mass to 50% by mass, even more preferably from 20% by mass to 40% by mass.
  • the binder polymer include the following compound A (Me represents a methyl group).
  • the content ratio of each structural unit shown below can be appropriately changed according to the purpose.
  • the binder polymer commercially available products may be used.
  • Acryt (registered trademark) 8KB-001 of Taisei Fine Chemical Co., Ltd. may be used. 8KB series.
  • the acid value of the binder polymer is preferably from 60 mgKOH / g to 250 mgKOH / g, more preferably from 70 mgKOH / g to 180 mgKOH / g.
  • the acid value is a value measured according to the method described in JIS K0070 (1992). The same applies hereinafter.
  • the binder polymer contains a binder polymer having an acid value of 60 mgKOH / g or more, in addition to the above-mentioned advantages, the first light-shielding layer and the light-shielding layer Between them can be improved.
  • any film-forming resin other than the above-mentioned polymers can be appropriately selected and used according to the purpose.
  • the weight average molecular weight of the binder polymer is not particularly limited, but is preferably more than 3,000, more preferably more than 3,000 and not more than 60,000, and more preferably 5,000 to 50,000. More preferred.
  • the measurement of the weight average molecular weight can be performed by gel permeation chromatography (GPC) by the same method and under the same conditions as the measurement of the weight average molecular weight of the binder polymer used in the light-shielding layer described later.
  • the binder polymer may be used alone, or may contain two or more kinds.
  • the content of the binder polymer in the first photosensitive layer is preferably from 10% by mass to 90% by mass, more preferably from 15% by mass to 80% by mass, based on the total mass of the first photosensitive layer, from the viewpoint of photosensitivity and the strength of the cured film. % By mass or less, more preferably 20% by mass or more and 70% by mass or less.
  • the first photosensitive layer contains at least one polymerizable compound.
  • the polymerizable compound is a component that contributes to the photosensitivity (that is, photocurability) of the first photosensitive layer and the strength of the cured film.
  • the polymerizable compound in the present disclosure is a compound having one or more ethylenically unsaturated groups (hereinafter, also referred to as “ethylenically unsaturated compound”).
  • the polymerizable compound is preferably a radical polymerizable compound that releases a radical as an active species by light irradiation.
  • the first photosensitive layer preferably contains a bifunctional or higher functional ethylenically unsaturated compound as the ethylenically unsaturated compound.
  • the bifunctional or higher functional ethylenically unsaturated compound means a compound having two or more ethylenically unsaturated groups in one molecule.
  • a (meth) acryloyl group is more preferred.
  • a (meth) acrylate compound is preferable.
  • the first photosensitive layer includes a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth) acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably And a (meth) acrylate compound having three or more functional groups).
  • a bifunctional ethylenically unsaturated compound preferably a bifunctional (meth) acrylate compound
  • a trifunctional or higher functional ethylenically unsaturated compound preferably And a (meth) acrylate compound having three or more functional groups
  • the bifunctional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds.
  • Examples of the bifunctional ethylenically unsaturated compound include tricyclodecane dimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,6-hexane. And diol di (meth) acrylate.
  • bifunctional ethylenically unsaturated compound more specifically, tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, new 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, new Nakamura Chemical Industry Co., Ltd.).
  • A-DCP tricyclodecane dimethanol diacrylate
  • DCP new 1,9-nonanediol diacrylate
  • A-HD-N new Nakamura Chemical Industry Co., Ltd.
  • the trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.
  • Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth) Examples include acrylate, ditrimethylolpropanetetra (meth) acrylate, isocyanuric acid (meth) acrylate, and a (meth) acrylate compound having a glycerin tri (meth) acrylate skeleton.
  • (tri / tetra / penta / hexa) (meth) acrylate” is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate.
  • (Tri / tetra) (meth) acrylate” is a concept including tri (meth) acrylate and tetra (meth) acrylate.
  • Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth) acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), Alkylene oxide-modified compound of (meth) acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex) Ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.
  • KYARAD registered trademark
  • DPCA-20 Alkylene oxide-modified compound of (meth) acrylate compound
  • ATM-35E Alkylene oxide-modified compound of (meth) acrylate compound
  • Examples of the ethylenically unsaturated compound also include a urethane (meth) acrylate compound (preferably a trifunctional or higher functional urethane (meth) acrylate compound).
  • Examples of trifunctional or higher functional urethane (meth) acrylate compounds include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.) Co., Ltd.).
  • the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group from the viewpoint of improving developability.
  • the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxy group, and a carboxy group is preferable.
  • PETA penta and hexaacrylate
  • DPHA dipentaerythritol penta and hexaacrylate
  • these trifunctional or more ethylenically unsaturated compounds having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group,
  • the ethylenically unsaturated compound having an acid group at least one selected from the group consisting of bifunctional or more functional ethylenically unsaturated compounds having a carboxy group and carboxylic anhydrides thereof is preferable. This increases the developability and the strength of the cured film.
  • the bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group is not particularly limited, and can be appropriately selected from known compounds.
  • Examples of the bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group include ARONIX (registered trademark) TO-2349ME (manufactured by Toagosei Co., Ltd.), ARONIX M-520 (manufactured by Toagosei Co., Ltd.), or And Aronix M-510 (manufactured by Toagosei Co., Ltd.) can be preferably used.
  • ARONIX registered trademark
  • TO-2349ME manufactured by Toagosei Co., Ltd.
  • ARONIX M-520 manufactured by Toagosei Co., Ltd.
  • And Aronix M-510 manufactured by Toagosei Co., Ltd.
  • the ethylenically unsaturated compound having an acid group is a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942.
  • the contents of this publication are incorporated into the present disclosure.
  • the weight average molecular weight (Mw) of the ethylenically unsaturated compound used in the present disclosure is preferably from 200 to 3,000, more preferably from 250 to 2,600, still more preferably from 280 to 2,200, and more preferably from 300 to 2,200. 200 is particularly preferred.
  • the proportion of the content of the ethylenically unsaturated compound having a molecular weight of 300 or less is relative to all the ethylenically unsaturated compounds contained in the first photosensitive layer.
  • the content is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.
  • Ethylenically unsaturated compounds may be used alone or in combination of two or more.
  • the content of the ethylenically unsaturated compound in the first photosensitive layer is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 70% by mass, and more preferably 20% by mass to the total mass of the first photosensitive layer. 60 mass% is more preferable, and 20 mass% to 50 mass% is particularly preferable.
  • the content of the bifunctional ethylenically unsaturated compound is included in the first photosensitive layer. 10% by mass to 90% by mass, more preferably 20% by mass to 85% by mass, even more preferably 30% by mass to 80% by mass, based on all the ethylenically unsaturated compounds obtained.
  • the content of the trifunctional or higher-functional ethylenically unsaturated compound is preferably from 10% by mass to 90% by mass, more preferably from 15% by mass to 90% by mass, based on all the ethylenically unsaturated compounds contained in the first photosensitive layer.
  • the content of the bifunctional or more ethylenically unsaturated compound is 40% by mass or more with respect to the total content of the bifunctional ethylenically unsaturated compound and the trifunctional or more ethylenically unsaturated compound. It is preferably less than 40% by mass, more preferably 40% by mass to 90% by mass, still more preferably 50% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass. .
  • the first photosensitive layer may further contain a monofunctional ethylenically unsaturated compound.
  • the bifunctional or higher functional ethylenically unsaturated compound is a main component in the ethylenically unsaturated compound contained in the first photosensitive layer. Is preferred.
  • the content of the bifunctional or higher functional ethylenically unsaturated compound is controlled by the ethylenically unsaturated compound contained in the first photosensitive layer. It is preferably from 40% by mass to 100% by mass, more preferably from 50% by mass to 100% by mass, particularly preferably from 60% by mass to 100% by mass, based on the total content of the saturated compound.
  • the first photosensitive layer contains an ethylenically unsaturated compound having an acid group (preferably, a bifunctional or more functional ethylenically unsaturated compound having a carboxy group or a carboxylic anhydride thereof).
  • the content of the ethylenically unsaturated compound is preferably 0.5% by mass to 50% by mass, more preferably 0.5% by mass to 20% by mass, and preferably 0.5% by mass to the total mass of the first photosensitive layer. % To 10% by mass is more preferred.
  • the first photosensitive layer contains at least one photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
  • Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as an “oxime-based photopolymerization initiator”) and a photopolymerization initiator having an ⁇ -aminoalkylphenone structure (hereinafter, “ ⁇ - Aminoalkylphenone-based photopolymerization initiator "), photopolymerization initiator having an ⁇ -hydroxyalkylphenone structure (hereinafter also referred to as” ⁇ -hydroxyalkylphenone-based polymerization initiator "), acylphosphine oxide structure (Hereinafter also referred to as “acylphosphine oxide-based photopolymerization initiator”), and a photopolymerization initiator having an N
  • the photopolymerization initiator is at least selected from the group consisting of an oxime-based photopolymerization initiator, an ⁇ -aminoalkylphenone-based photopolymerization initiator, an ⁇ -hydroxyalkylphenone-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator. It is preferable to include at least one kind, more preferably at least one selected from the group consisting of an oxime-based photopolymerization initiator, an ⁇ -aminoalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator. .
  • the photopolymerization initiator for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-014783 may be used.
  • photopolymerization initiators include 1- [4- (phenylthio)]-1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE® OXE-01, BASF) 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) (trade name: IRGACURE @ OXE-02, manufactured by BASF) 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE @ 379EG, BASF), 2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE @ 907, manufactured by BASF), 2- Droxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-pro
  • the photopolymerization initiator may be used alone or in combination of two or more.
  • the content of the photopolymerization initiator in the first photosensitive layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more based on the total mass of the first photosensitive layer. Further, the content of the photopolymerization initiator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the first photosensitive layer.
  • the first photosensitive layer can contain at least one surfactant.
  • the surfactant for example, the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362, known fluorine-based surfactants, and the like can be used.
  • a fluorine-based surfactant is preferable. Examples of commercially available fluorine-based surfactants include Megafac (registered trademark) F-551A (manufactured by DIC Corporation).
  • the content of the surfactant in the first photosensitive layer is preferably 0.01% by mass to 3% by mass based on the total mass of the first photosensitive layer. , 0.05% by mass to 1% by mass, more preferably 0.1% by mass to 0.8% by mass.
  • the first photosensitive layer may contain other components such as additives, if necessary, in addition to the components described above.
  • the photosensitive layer can further contain a blocked isocyanate compound from the viewpoint of hardness after curing.
  • the blocked isocyanate compound means a "compound having a structure in which an isocyanate group of isocyanate is protected (masked) with a blocking agent".
  • the dissociation temperature of the blocked isocyanate compound is preferably from 100 ° C to 160 ° C, more preferably from 130 ° C to 150 ° C.
  • the dissociation temperature of a blocked isocyanate in the present specification is defined as "a deprotection reaction of a blocked isocyanate when measured by a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.) by DSC (Differential scanning calorimetry) analysis". Accompanying endothermic peak temperature ".
  • an oxime compound or a pyrazole compound is preferable, and an oxime compound is particularly preferable.
  • the blocked isocyanate compound has an isocyanurate structure from the viewpoint of improving the brittleness of the film, improving the adhesion to the transfer target, and the like.
  • the blocked isocyanate compound having an isocyanurate structure can be prepared, for example, by protecting hexamethylene diisocyanate by isocyanuration.
  • compounds having an oxime structure using an oxime compound as a blocking agent are more likely to have a dissociation temperature in a preferable range than compounds having no oxime structure, and are likely to reduce development residues. Is preferred.
  • the blocked isocyanate compound used in the present disclosure preferably has a radical polymerizable group from the viewpoint of hardness after curing.
  • the radical polymerizable group is not particularly limited, and a known polymerizable group can be used. Examples thereof include an ethylenically unsaturated group such as a (meth) acryloxy group, a (meth) acrylamide group, a styryl group, and a glycidyl group. And a group having an epoxy group.
  • the polymerizable group is preferably an ethylenically unsaturated group, and more preferably a (meth) acryloxy group, from the viewpoint of the surface condition, development speed and reactivity of the obtained cured film.
  • blocked isocyanate compound used in the present disclosure a commercially available blocked isocyanate compound can also be mentioned.
  • a commercially available blocked isocyanate compound can also be mentioned.
  • Karenz AOI-BM, Karenz MOI-BM, Karenz MOI-BP (all manufactured by Showa Denko KK), block type duranate series (manufactured by Asahi Kasei Chemicals Corporation) and the like can be mentioned.
  • the blocked isocyanate compound used in the present disclosure preferably has a molecular weight of 200 to 3,000, more preferably 250 to 2,600, and particularly preferably 280 to 2,200.
  • one type of blocked isocyanate compound may be used alone, or two or more types may be used in combination.
  • the content of the blocked isocyanate compound is preferably from 1% by mass to 50% by mass, more preferably from 5% by mass to 30% by mass, based on the total mass of the first photosensitive layer.
  • the first photosensitive layer may contain at least one polymerization inhibitor.
  • a thermal polymerization inhibitor also referred to as a polymerization inhibitor
  • 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 more preferably 0.01% by mass to 3% by mass based on the total mass of the first photosensitive layer. 1% by mass is more preferable, and 0.01% by mass to 0.8% by mass is further preferable.
  • the first photosensitive layer can further contain a hydrogen donating compound.
  • the hydrogen-donating compound has effects such as further improving the sensitivity of the photopolymerization initiator to actinic rays or suppressing polymerization inhibition of the polymerizable compound by oxygen.
  • Examples of the hydrogen donating compound include amines such as M.P. R. Sander et al., "Journal of Polymer Society", vol. 10, p. 3173 (1972), JP-B-44-20189, JP-A-51-82102, JP-A-52-134692, and JP-A-59-138205.
  • JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, and Research Disclosure 33825 Specific examples include triethanolamine. , P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.
  • hydrogen donating compound examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate, etc.), and JP-B-55 And hydrogen compounds described in JP-A-6-308727 (eg, trithiane).
  • amino acid compounds eg, N-phenylglycine
  • organometallic compounds described in JP-B-48-42965 eg, tributyltin acetate, etc.
  • JP-B-55 And hydrogen compounds described in JP-A-6-308727 eg, trithiane
  • the content of these hydrogen-donating compounds is preferably in the range of 0.1% by mass or more and 30% by mass or less based on the total mass of the first photosensitive layer from the viewpoint of improving the curing speed by the balance between the polymerization growth rate and the chain transfer.
  • the range is preferably from 1% by mass to 25% by mass, more preferably from 0.5% by mass to 20% by mass.
  • the first photosensitive layer may contain other components other than the components described above.
  • the other components include a thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784, and other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.
  • the first photosensitive layer may include at least one kind of particles (for example, metal oxide particles) as another component for the purpose of adjusting the refractive index and the light transmittance.
  • Metals constituting the metal oxide particles include semimetals such as B, Si, Ge, As, Sb, and Te.
  • the average primary particle diameter of the particles is preferably from 1 nm to 200 nm, more preferably from 3 nm to 80 nm. The average primary particle diameter is calculated by measuring the particle diameter of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. If the shape of the particles is not spherical, the longest side is the particle diameter.
  • the content of the particles is preferably 0% by mass to 35% by mass, more preferably 0% by mass to 10% by mass, still more preferably 0% by mass to 5% by mass, based on the total mass of the first photosensitive layer.
  • the content is more preferably from 1% by mass to 1% by mass, and particularly preferably 0% by mass (that is, no particles are contained in the first photosensitive layer).
  • the first photosensitive layer may contain a trace amount of a coloring agent (a pigment, a dye, or the like) as another component, but it is preferable that the first photosensitive layer does not substantially contain a coloring agent from the viewpoint of transparency.
  • the content of the colorant in the first photosensitive layer is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the first photosensitive layer.
  • the first photosensitive layer preferably has a low impurity content.
  • impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and their ions, as well as free halogen and halide ions (chloride Ion, bromide ion, iodide ion, etc.).
  • the content of the impurities in the first photosensitive layer is preferably 1000 ppm or less, more preferably 200 ppm or less, and still more preferably 40 ppm or less on a mass basis.
  • the lower limit is not particularly defined, it can be set to 10 ppb or more and 100 ppb or more on a mass basis from the viewpoint of a limit that can be practically reduced and a measurement limit.
  • a method of reducing impurities to the above range there can be mentioned, for example, selecting a raw material of a resin and an additive that does not contain impurities, preventing mixing of impurities at the time of forming a layer, and the like. By such a method, the amount of impurities can be kept within the above range.
  • the impurities can be quantified by a known method such as ICP (Inductively Coupled Plasma) emission spectroscopy and atomic absorption spectroscopy.
  • the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide and hexane in the first photosensitive layer is small. Is preferred.
  • the content of these compounds in the first photosensitive layer is preferably 1000 ppm or less, more preferably 200 ppm or less, even more preferably 40 ppm or less, on a mass basis.
  • the lower limit is not particularly defined, it can be set to 10 ppb or more and 100 ppb or more on a mass basis from the viewpoint of a limit that can be practically reduced and a measurement limit.
  • the content of the impurities can be suppressed in the same manner as the above-described metal impurities. In addition, it can be quantified by a known measuring method.
  • the thickness of the first photosensitive layer is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and particularly preferably 12 ⁇ m or less.
  • the thickness of the first photosensitive layer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and particularly preferably 3 ⁇ m or more from the viewpoint of production suitability.
  • the refractive index of the first photosensitive layer is preferably from 1.47 to 1.56, more preferably from 1.50 to 1.53, even more preferably from 1.50 to 1.52, and preferably from 1.51 to 1.52. Particularly preferred.
  • “refractive index” refers to a refractive index at a wavelength of 550 nm.
  • the “refractive index” in the present disclosure means a value measured by ellipsometry with visible light having a wavelength of 550 nm at a temperature of 23 ° C., unless otherwise specified.
  • the method for forming the first photosensitive layer is not particularly limited, and a known method can be used.
  • a composition for forming a first photosensitive layer (a composition for a first photosensitive layer) containing a solvent is applied onto a temporary support by a method such as coating, and the method is applied. And a method of forming by drying.
  • the composition for the first photosensitive layer mixes at least other components such as a binder polymer, a polymerizable compound, a photopolymerization initiator and a solvent (particularly an organic solvent), and, if necessary, a surfactant and an additive. Can be prepared.
  • a known method can be used as a coating method, and examples thereof include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method). And a die coating method is preferred.
  • a drying method known methods such as natural drying, heat drying, and drying under reduced pressure can be applied alone or in combination.
  • the solvent used in the composition for the first photosensitive layer a commonly used solvent can be used without any particular limitation.
  • an organic solvent is preferable.
  • the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (alias: 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam , N-propanol, 2-propanol and the like.
  • the solvent may be used as a mixed solvent obtained by mixing two or more kinds of organic solvents.
  • the mixed solvent a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate, or a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate is preferable.
  • the solid content of the composition for the first photosensitive layer is preferably 5% by mass to 80% by mass, more preferably 5% by mass to 40% by mass, based on the total amount of the composition for the first photosensitive layer. 5% to 30% by mass is particularly preferred.
  • the viscosity (25 ° C.) of the composition for the first photosensitive layer is preferably from 1 mPa ⁇ s to 50 mPa ⁇ s, more preferably from 2 mPa ⁇ s to 40 mPa ⁇ s, and preferably from 3 mPa ⁇ s, from the viewpoint of applicability. S to 30 mPa ⁇ s is more preferable.
  • the viscosity is a value measured using, for example, VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.).
  • the surface tension (25 ° C.) of the composition for the first photosensitive layer is preferably from 5 mN / m to 100 mN / m from the viewpoint of applicability, and is preferably from 10 mN / m to 10 mN / m. 80 mN / m is more preferable, and 15 mN / m to 40 mN / m is particularly preferable.
  • the surface tension is a value measured by using, for example, an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).
  • Solvents described in paragraphs 0054 and 0055 of US Patent Application Publication No. 2005/282073 can also be used as the solvent, the contents of which are incorporated herein. Further, as the solvent, an organic solvent having a boiling point of 180 ° C. to 250 ° C. (high boiling point solvent) can be used as necessary.
  • the light-shielding layer is a layer having a light-blocking property arranged on the side opposite to the side having the temporary support of the first photosensitive layer, contains at least a binder polymer, and is formed with an optical density of 0.5 or more. It is a thing.
  • the light-shielding layer preferably contains, in addition to the binder polymer, an ultraviolet absorbing material.If necessary, the light-shielding layer may contain a curing component, and may contain other components such as a surfactant, a solvent, and an additive. Is also good.
  • the curing component includes a polymerizable compound, a photopolymerization initiator, and the like.
  • the light shielding layer has an optical density of 0.5 or more.
  • the optical density is 0.5 or more, light over a wide wavelength range is easily absorbed, and the amount of light transmitted from one side of the light-shielding layer to the other side can be reduced. Thereby, the influence of light from the other side on the photosensitive layer disposed on one side of the transparent substrate can be reduced.
  • the higher the optical density the more preferable it is.
  • the optical density can be set to, for example, 6.0 or less or 5.0 or less from the viewpoint of easy design of the prescription of the light shielding layer.
  • the optical density is measured by preparing a laminate having a laminated structure of a temporary support / light-shielding layer / glass substrate, and measuring the optical density of the laminate using a transmission densitometer (BMT-1, manufactured by Sakata Inx Engineering). Measure.
  • BMT-1 transmission densitometer
  • the optical density of the temporary support and the glass substrate used for the laminate is measured by the same method. Then, the optical density of the temporary support and the glass substrate is subtracted from the optical density of the laminate to obtain the optical density of the light-shielding layer.
  • the light-shielding layer contains at least one binder polymer.
  • the binder polymer is preferably a resin that can be dissolved by contact with an alkaline solvent (so-called alkali-soluble resin).
  • binder polymer examples include resins described in paragraph 0025 of JP-A-2011-95716 and paragraphs 0033 to 0052 of JP-A-2010-237589.
  • the light-shielding layer preferably contains a binder polymer having a carboxy group, and particularly preferably contains a carboxy-group-containing acrylic resin having an acid value of 60 mgKOH / g or more, from the viewpoint of better pattern formability.
  • the acid value of the binder polymer is preferably from 60 mgKOH / g to 250 mgKOH / g, and more preferably from 70 mgKOH / g to 180 mgKOH / g.
  • the edge roughness refers to an edge of a pattern observed using a laser microscope (for example, VK-9500, Keyence Corporation, objective lens 50 times), and the most swelled portion of the pattern edge in the field of view ( With the difference between the peak (top of the mountain) and the most constricted portion (bottom of the valley) as the absolute value, the absolute value is determined for five different locations, the average value of the five locations is calculated, and the calculated value is meant.
  • binder polymer examples include a random copolymer of benzyl (meth) acrylate / (meth) acrylic acid, a random copolymer of styrene / (meth) acrylic acid, and cyclohexyl (meth) acrylate / (meth) acrylic.
  • a random copolymer of benzyl (meth) acrylate / (meth) acrylic acid is preferred from the viewpoint of developability.
  • binder polymer commercially available products may be used.
  • Acrybase registered trademark
  • Acryt (registered trademark) 8KB-001 of Taisei Fine Chemical Co., Ltd. may be used. 8KB series.
  • the weight average molecular weight (Mw) of the binder polymer is preferably from 4,000 to 25,000, more preferably from 4,000 to 20,000, still more preferably from 5,000 to 18,000.
  • Mw weight average molecular weight
  • the weight average molecular weight of the binder polymer is 4000 or more, the removability of the first photosensitive layer during development becomes good. Furthermore, since the tackiness of the formed pattern is suppressed, when the transfer film has a protective film, the peelability of the protective film when peeling off the protective film is improved. On the other hand, when the weight average molecular weight of the binder polymer is 25,000 or less, the heat sagging property is improved, and the generation of development residues is suppressed.
  • the weight average molecular weight of the binder polymer can be measured by gel permeation chromatography (GPC) under the following conditions.
  • the calibration curve is "Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40", “F-20”, “F-4”, “F-1”, “A-5000”, “A -2500 ",” A-1000 ", and” n-propylbenzene ".
  • the acid value of the binder polymer is a value determined according to the method described in JIS K0070 (1992).
  • the content of the binder polymer in the light-shielding layer is preferably from 10% by mass to 70% by mass, more preferably from 15% by mass to 60% by mass, and still more preferably from 20% by mass to 50% by mass, based on the total solid content of the light-shielding layer. .
  • the light shielding layer further contains at least one kind of ultraviolet absorbing material.
  • the ultraviolet light refers to light having a wavelength in the range of 250 nm to 400 nm.
  • the ultraviolet absorbing material is not limited as long as it has a property of absorbing ultraviolet rays, and examples thereof include pigments (especially black pigments) and materials called ultraviolet absorbers having an absorption maximum between 250 nm and 400 nm. Can be
  • the black pigment is not particularly limited as long as it can exhibit light-shielding properties in the light-shielding layer.
  • a known black pigment for example, a black pigment selected from organic pigments and inorganic pigments can be suitably used.
  • Inorganic pigments include pigments containing metal compounds such as metal pigments and metal oxide pigments. From the viewpoint that the optical density of the formed light-shielding layer is good, examples of the black pigment include titanium oxide pigments such as carbon black, titanium carbon, iron oxide, and titanium black, and graphite.
  • the light-shielding layer according to the present disclosure includes carbon black as the ultraviolet absorbing material.
  • Carbon black is also available as a commercial product, and examples thereof include a black pigment dispersion FDK-911 [trade name: FDK-911] manufactured by Tokyo Ink.
  • the carbon black is preferably a carbon black whose surface is coated with a resin (hereinafter, also referred to as a resin-coated carbon black) from the viewpoint that the uniform dispersibility of the carbon black in the light-shielding layer becomes better.
  • the resin may be coated with the carbon black as long as at least a part of the surface of the carbon black is coated, and the entire surface may be coated.
  • the resin-coated carbon black can be produced, for example, by the method described in paragraphs 0036 to 0042 of Japanese Patent No. 5320652. It is also available as a commercial product, for example, SF Black GB4051 manufactured by Sanyo Dyeing Co., Ltd. and the like.
  • the particle diameter of the black pigment is preferably from 0.001 ⁇ m to 0.3 ⁇ m, more preferably from 0.01 ⁇ m to 0.2 ⁇ m in terms of number average particle diameter from the viewpoint of dispersion stability.
  • the “particle size” refers to the diameter of an electron micrograph image of a particle when it is formed into a circle of the same area, and the “number average particle size” refers to the particle size of any 100 particles, Mean.
  • the number average particle diameter of the black pigment contained in the light-shielding layer is included in the viewing angle by using a photograph of the light-shielding layer containing the black pigment taken at a magnification of 300,000 with a transmission electron microscope (JEOL).
  • the particle diameter of any 100 particles can be measured and calculated as the average of the measured values.
  • non-black pigment examples include pigments described in JP-A-2008-224982, paragraphs 0030 to 0044, which exhibit a hue other than black; I. Pigment Green 58, C.I. I. Pigment Blue 79 in which the chloro group (Cl) is changed to a hydroxyl group (OH).
  • the pigment that can be included in the light-shielding layer is not limited to the above pigment.
  • UV absorber having an absorption maximum between 250 nm and 400 nm examples include Sumisorb 130 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (all manufactured by Taiwan Eiko Chemical Co., Ltd.), and Tomissorb 800 (AP Benzophenone compounds such as SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by Cipro Kasei Co., Ltd.); (The above are manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80 JF83 (all manufactured by Johoku Chemical Industry Co., Ltd.), TINUVIN @ PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN900, TINUVIN928,
  • the content of the ultraviolet absorbing material in the light-shielding layer (the content of the black pigment when the light-shielding layer contains only a black pigment, and the total mass of the black pigment and the pigment other than black when the light-shielding layer contains only a black pigment) is determined by the total solid content of the light-shielding layer.
  • the amount is preferably from 10% by mass to 70% by mass, more preferably from 20% by mass to 60% by mass, and still more preferably from 20% by mass to 45% by mass, based on the amount.
  • the content of the ultraviolet absorbing material is 10% by mass or more, the optical density of the light shielding layer can be increased while keeping the film thickness small.
  • the content of the ultraviolet absorbing material is 70% by mass or less, the curing sensitivity at the time of patterning the light shielding layer becomes good.
  • the light-shielding layer preferably further contains at least one polymerizable compound as a curing component. If the light-shielding layer contains a polymerizable compound, the solubility at the time of development will be excellent.
  • the polymerizable compound is a compound having at least one polymerizable group in a molecule, and may be either a monomer or a polymer. Monomer) is more preferred. There is no particular limitation on the type of the polymerizable group.
  • Examples of the polymerizable group include an ethylenically unsaturated group and an epoxy group.
  • An ethylenically unsaturated group is preferable, and a (meth) acryloyl group is more preferable.
  • the polymerizable compound is preferably a bifunctional or higher (polyfunctional) polymerizable monomer having two or more polymerizable groups, and more preferably a bifunctional polymerizable monomer.
  • a polyfunctional polymerizable monomer generation of a development residue when developing the light shielding layer can be suppressed.
  • a bifunctional polymerizable monomer generation of a development residue can be suppressed even in development with a weak alkaline developer (for example, an aqueous solution of sodium carbonate).
  • polymerizable compound examples include monofunctional acrylates or monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, Xanediol di (meth) acrylate, trimethylolpropane tri (acryloyl
  • a urethane (meth) acrylate compound is preferred from the viewpoint of layer flexibility.
  • polymerizable compound commercially available products may be used.
  • commercially available products include tricyclodecane dimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Co., Ltd., bifunctional, molecular weight 304), tricyclodecane dimenanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., Ltd.) Co., Ltd., bifunctional, molecular weight 332), 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd., bifunctional, molecular weight 268), 1,6-hexanediol diacrylate (A -HD-N, Shin-Nakamura Chemical Co., Ltd., bifunctional, molecular weight 226), 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (A-BPEF, Shin-Nakamura Chemical Co., Ltd.) Bifunctional, molecular weight
  • the molecular weight of the polymerizable compound is preferably 3,000 or less, more preferably 2,000 or less, further preferably 1,000 or less, and particularly preferably 500 or less.
  • the molecular weight of the polymerizable compound is 500 or less, heat dripping is likely to occur in heat treatment at a low temperature.
  • a bifunctional polymerizable monomer having a molecular weight of 500 or less is preferable.
  • the molecular weight of the polymerizable compound is determined by identifying the molecular structure by mass spectrometry (for example, liquid chromatography (LC / MS) analysis, gas chromatography (GC / MS) analysis, high-speed atom collision chromatography (FAB / MS analysis), etc.). , Can be determined from the molecular formula.
  • mass spectrometry for example, liquid chromatography (LC / MS) analysis, gas chromatography (GC / MS) analysis, high-speed atom collision chromatography (FAB / MS analysis), etc.
  • the polymerizable compound may be used alone or in combination of two or more. Among them, it is preferable to use a combination of two or more polymerizable compounds from the viewpoint of removability during development. Further, it is preferable to use a bifunctional polymerizable compound and a non-bifunctional polymerizable compound in combination from the viewpoint of suppression of residues during development (preferably carbonic acid development) and film strength.
  • the content of the polymerizable compound contained in the light-shielding layer is preferably 0% by mass to 50% by mass, more preferably 0% by mass to 40% by mass, and more preferably 0% by mass to 30% by mass based on the total solid content of the composition. % Is more preferred.
  • the bifunctional polymerizable with respect to the total mass of the polymerizable compound (the total amount of the bifunctional polymerizable compound and the non-bifunctional polymerizable compound)
  • the mass ratio of the compounds (bifunctional polymerizable compound / total polymerizable compound) is preferably 50% by mass or more.
  • a content of (bifunctional polymerizable compound / total of polymerizable compound) of 50% by mass or more is advantageous in terms of suppressing a development residue by a weak alkali developing solution (for example, aqueous sodium carbonate solution) and film strength.
  • the mass ratio (M / B ratio) of the content (M) of the polymerizable compound to the content (B) of the binder polymer is preferably 0.50 or less.
  • M / B ratio 0.50 or less, the linearity of the formed pattern becomes better.
  • the light-shielding layer may further contain at least one photopolymerization initiator as a curing component. This is effective in improving the pattern shape after development.
  • the photopolymerization initiator is contained too much, the polymerization reaction of the light-shielding layer proceeds even when the light irradiated from the other side reaches one side, for example, and the polymerization reaction is close to the transparent substrate. Therefore, residues of the light-shielding layer after development (removal residue of the light-shielding layer during development (so-called fog)) may easily occur.
  • the content of the photopolymerization initiator in the light-shielding layer is preferably 1% by mass or less based on the total solid content of the light-shielding layer, from the viewpoint of suppressing deterioration of the residue of the light-shielding layer in the light irradiation region.
  • the content of the photopolymerization initiator is more preferably less than 0.5% by mass, and further preferably 0% by mass (not contained).
  • photopolymerization initiator examples include photopolymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716, and oxime-based photopolymerization initiators described in paragraphs 0064 to 0081 of JP-A-2015-014783.
  • photopolymerization initiator commercially available products may be used.
  • Examples of commercially available products include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (trade name: IRGACURE OXE-01, BASF), 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), 2- (dimethylamino)- 2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379EG, manufactured by BASF), 2-methyl-1- (4-methylthio) Phenyl) -2-morpholinopropan-1-one (trade name: IRGACURE 907, manufactured by BASF), 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benz
  • the light-shielding layer can contain at least one surfactant.
  • the surfactant include the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.
  • a fluorine-based surfactant for example, Megafac (registered trademark) F-784-F, F-780F, F-555A, etc., manufactured by DIC Corporation
  • F-784-F for example, Megafac (registered trademark) F-784-F, F-780F, F-555A, etc., manufactured by DIC Corporation
  • the content of the surfactant in the light-shielding layer is preferably 0.01% by mass to 3% by mass, and more preferably 0.05% by mass, based on the total mass of the light-shielding layer. 11% by mass is more preferable, and 0.1 to 0.8% by mass is further preferable.
  • the light-shielding layer may contain other components such as a polymerization inhibitor, a dye, and an additive, if necessary, in addition to the components described above.
  • the light-shielding layer preferably contains at least one polymerization inhibitor.
  • a polymerization inhibitor for example, a thermal polymerization inhibitor (also referred to as a polymerization inhibitor) described in paragraph 0018 of Japanese Patent No. 4502784 can be used.
  • phenothiazine, hydroquinone monomethyl ether, and the like can be suitably used as the polymerization inhibitor.
  • the light-shielding layer may contain a dye from the viewpoint of exhibiting antireflection ability.
  • a dye from the viewpoint of exhibiting antireflection ability.
  • known dyes for example, known dyes described in documents such as “Dye Handbook” (edited by the Society of Organic Synthetic Chemistry, published in 1970), or A commercially available dye can be appropriately selected and used.
  • the dye examples include an azo dye, a metal complex salt azo dye, a pyrazolone azo dye, a naphthoquinone dye, an anthraquinone dye, a phthalocyanine dye, a carbonium dye, a quinone imine dye, a methine dye, a cyanine dye, a squarylium dye, a pyrylium salt, and a metal thiolate complex.
  • Dyes examples include an azo dye, a metal complex salt azo dye, a pyrazolone azo dye, a naphthoquinone dye, an anthraquinone dye, a phthalocyanine dye, a carbonium dye, a quinone imine dye, a methine dye, a cyanine dye, a squarylium dye, a pyrylium salt, and a metal thiolate complex. Dyes.
  • the content of the dye is preferably 1 part by mass to 40 parts by mass with respect to 100 parts by mass of the above-described pigment from the viewpoint of exhibiting antireflection ability. More preferably, the amount is from 20 parts by mass to 20 parts by mass.
  • the content of the dye is in the above range, the anti-reflection effect of the formed light-shielding layer, that is, the effect of visually suppressing glare is improved.
  • additive examples include other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.
  • the light-shielding layer preferably has a low impurity content.
  • the details of the impurities in the light-shielding layer and the details of preferred embodiments and the like are the same as in the case of the above-described first photosensitive layer, and thus description thereof is omitted here.
  • the thickness of the light-shielding layer is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less. When the thickness of the light-shielding layer is 20 ⁇ m or less, it is advantageous in terms of making the entire transfer film thinner.
  • the thickness of the light-shielding layer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, from the viewpoint of production suitability.
  • the method for forming the light-shielding layer is not particularly limited, and a known method can be used.
  • Examples of the method for forming the light-shielding layer include, for example, a composition for a light-shielding layer containing a solvent on the surface of the above-described first photosensitive layer, or on the surface of the intermediate layer when the first photosensitive layer has an intermediate layer. Is applied by a method such as coating and dried if necessary.
  • the composition for a light-shielding layer can be prepared by mixing at least a binder polymer and a solvent (particularly an organic solvent), and if necessary, other components such as a curing component, a surfactant and an additive.
  • the method of coating and the method of drying are the same as in the case of the above-described first photosensitive layer, and a known method can be applied.
  • the method is used for coating and drying of the above-described first photosensitive layer.
  • a method similar to the method can be used.
  • the black pigment is desirably used in the composition for the light-shielding layer as a dispersion in which the black pigment is dispersed.
  • the dispersion can be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent or a vehicle described below and dispersing the mixture.
  • the vehicle refers to a medium portion in which the pigment is dispersed, and includes a binder component which is liquid and binds to the black pigment to form a layer, and a medium such as an organic solvent which dissolves and dilutes the binder component.
  • the dispersing machine used for dispersing the black pigment is not particularly limited.
  • Known dispersers such as a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill are exemplified.
  • the black pigment which is a dispersoid, may be finely pulverized by mechanical grinding described on page 310 using frictional force.
  • a pigment dispersing agent according to the kind of a pigment and an organic solvent, For example, a commercially available dispersing agent can be used.
  • a commonly used organic solvent can be used without any particular limitation, and examples thereof include esters, ethers, ketones, and aromatic hydrocarbons.
  • the solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PEGMEA), cyclohexanone, cyclohexanol, and methyl isobutyl as in Solvent described in paragraphs 0054 and 0055 of US Patent Publication 2005/280733. Ketone, ethyl lactate, methyl lactate and the like can be used.
  • examples of the solvent include 1-methoxy-2-propyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, Preferred are cyclohexanone, diethylene glycol monoethyl ether acetate (ethyl carbitol acetate), diethylene glycol monobutyl ether acetate (butyl carbitol acetate), propylene glycol methyl ether acetate, methyl ethyl ketone, and the like.
  • the solvent may be used alone or in combination of two or more.
  • an organic solvent having a boiling point of 180 ° C. to 250 ° C. (high boiling point solvent) can be used as necessary.
  • the solid content of the composition for a light-shielding layer is preferably from 5% by mass to 80% by mass, more preferably from 5% by mass to 40% by mass, based on the total amount of the composition for a light-shielding layer. -30% by weight is particularly preferred.
  • An embodiment in which an intermediate layer is further provided between the first photosensitive layer and the light-shielding layer is preferable.
  • the intermediate layer between the first photosensitive layer and the light-shielding layer, the movement of the photopolymerization initiator in the first photosensitive layer to the light-shielding layer during storage after coating can be suppressed.
  • the photopolymerization initiator moves from the first photosensitive layer to the light-shielding layer and mixes, and the content ratio of the photopolymerization initiator in the light-shielding layer increases, light from the side of the transparent substrate that does not have the light-shielding layer becomes transparent.
  • the intermediate layer preferably contains a binder polymer, more preferably a binder polymer having solubility in water or a lower alcohol having 1 to 4 carbon atoms, and more preferably contains a binder polymer and a polymerizable compound. More preferred.
  • the intermediate layer preferably contains a binder polymer having solubility in water or a lower alcohol having 1 to 4 carbon atoms as a main component.
  • a binder polymer having solubility in water or a lower alcohol having 1 to 4 carbon atoms as a main component.
  • binder polymer contained most in the binder component contained in the intermediate layer or the content ratio of the binder component contained in the entire intermediate layer Is 50% by mass or more of the binder polymer.
  • the binder polymer having solubility in water or a lower alcohol having 1 to 4 carbon atoms can be appropriately selected from known ones, and examples thereof include polyvinyl alcohol and polyvinyl pyrrolidone. Among them, a combination of polyvinyl alcohol and polyvinylpyrrolidone is preferable as the binder polymer used for the intermediate layer.
  • “has solubility in water or a lower alcohol having 1 to 4 carbon atoms” means that 5 g or more is dissolved in 100 ml of water or a lower alcohol having 1 to 4 carbon atoms at 25 ° C.
  • examples of the water include ion-exchanged water and distilled water.
  • the lower alcohol having 1 to 4 carbon atoms includes, for example, methanol, ethanol, propanol, isopropanol and butanol.
  • the content of the binder polymer contained in the intermediate layer is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total solid content of the intermediate layer.
  • the upper limit is not particularly limited, and may be adjusted within a range of 100% by mass or less.
  • the intermediate layer preferably further contains at least one polymerizable compound. It is preferable to contain a polymerizable compound from the viewpoint of suppressing residues during development (preferably, carbon dioxide development).
  • the same compound as the polymerizable compound that can be used for the first photosensitive layer or the light-shielding layer can be appropriately selected and used, and a polymerizable monomer is preferable.
  • acrylamide monomers for example, FAM-401, FAM-301, FAM-201, FAM-402, etc., manufactured by Fuji Film Co., Ltd.
  • the polymerizable compound may be used alone or in combination of two or more.
  • the content of the polymerizable compound contained in the intermediate layer is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total solid content of the intermediate layer.
  • the intermediate layer may further include at least one photopolymerization initiator.
  • the photopolymerization initiator that can be used for the intermediate layer for example, the same photopolymerization initiator that can be used for the first photosensitive layer or the light-shielding layer can be appropriately selected and used.
  • the intermediate layer contains a photopolymerization initiator, it is effective in improving the pattern shape after development.
  • the content of the photopolymerization initiator contained in the intermediate layer is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total solid content of the intermediate layer.
  • the intermediate layer can contain at least one surfactant.
  • a fluorine-containing surfactant eg, Megafac (registered trademark) F-784F, F-780F, F-780F, F-780F, -444 etc.
  • the content of the surfactant contained in the intermediate layer is preferably from 0.001% by mass to 1% by mass, more preferably from 0.001% by mass to 0.5% by mass, based on the total solid content of the intermediate layer, 0.001% by mass to 0.1% by mass is more preferred.
  • the intermediate layer may include other components such as additives as necessary.
  • the additives are the same as the additives that can be added to the light shielding layer.
  • the thickness of the intermediate layer is preferably 0.2 ⁇ m to 5 ⁇ m, more preferably 0.5 ⁇ m to 3 ⁇ m, and still more preferably 0.8 ⁇ m to 2 ⁇ m.
  • the method for forming the intermediate layer is not particularly limited, and a known method can be used.
  • the method for forming the intermediate layer include a method in which the intermediate layer composition containing a solvent is applied to the surface of the above-described first photosensitive layer by a method such as coating, and dried if necessary.
  • the composition for an intermediate layer can be prepared by mixing at least a binder polymer and an aqueous solvent, and if necessary, other components such as a curing component, a surfactant and an additive.
  • the aqueous solvent include water, and a mixed solvent of water and an organic solvent capable of being water.
  • the composition for the intermediate layer is preferably an aqueous composition.
  • the method of coating and the method of drying are the same as in the case of the above-described first photosensitive layer, and a known method can be applied.
  • the method is used for coating and drying of the above-described first photosensitive layer.
  • a method similar to the method can be used.
  • the transfer film of the present disclosure may have a protective film on the surface of the light-shielding layer laminated on the temporary support.
  • a protective film By providing the protective film, it is possible to protect from contamination by impurities such as foreign matter and damage to the exposed surface during storage.
  • the protective film is preferably one that can be easily peeled off from the light-shielding layer, and the same or similar base material as the temporary support described later can be used.
  • the protective film include a polyolefin film (for example, a polypropylene (PP) film, a polyethylene (PE) film or the like), a polyethylene terephthalate (PET) film, silicon paper, a polytetrafluoroethylene film, or the like.
  • PP polypropylene
  • PE polyethylene
  • PET polyethylene terephthalate
  • the protective films described in paragraphs 0083 to 0087 and 0093 of JP-A-2006-259138 can be appropriately used.
  • the thickness of the protective film is preferably from 0.2 ⁇ m to 40 ⁇ m, more preferably from 0.5 ⁇ m to 30 ⁇ m.
  • the temporary support is preferably a resin substrate in terms of peeling from the transfer film, and more preferably a substrate using a material exhibiting flexibility after molding.
  • the substrate may be either a film or a sheet.
  • the temporary support may have transparency or may be colored (for example, colored by containing dyed silicon, alumina sol, chromium salt, zirconium salt, etc.).
  • the temporary support examples include a cycloolefin copolymer substrate, a polyethylene terephthalate (PET) substrate, a cellulose triacetate substrate, a polystyrene substrate, and a polycarbonate substrate.
  • PET polyethylene terephthalate
  • a PET substrate Is particularly preferred.
  • a temporary support having conductivity is also suitable, and the conductivity may be provided by, for example, the method described in JP-A-2005-221726.
  • the thickness of the temporary support is preferably 5 ⁇ m to 60 ⁇ m, more preferably 5 ⁇ m to 40 ⁇ m.
  • the transfer film of the present disclosure may include at least a first photosensitive layer and a light shielding layer on a temporary support, and may have an intermediate layer between the first photosensitive layer and the light shielding layer.
  • the transfer film 10 has a laminated structure in which a first photosensitive layer 17, an intermediate layer 15, a light shielding layer 13, and a protective film 11 are laminated on a temporary support 19 in this order from the temporary support. Have. By providing the intermediate layer 15 between the first photosensitive layer 17 and the light-shielding layer 13, the movement of the photopolymerization initiator from the first photosensitive layer 17 to the light-shielding layer 13 is suppressed.
  • the transfer film is not limited to the laminated structure shown in FIG. 1, but may be a laminated structure having no intermediate layer as shown in the laminated body in FIG.
  • the transfer film according to an embodiment of the present disclosure can be used, for example, as a transfer film for forming a wiring pattern of a metal wiring substrate provided in an image display device such as a touch panel.
  • a method of transferring a first photosensitive layer, a light-shielding layer, and the like to a transparent substrate using the transfer film of the present disclosure to form a pattern will be described later.
  • the transfer film can be stored by a known method. At the time of storage, the atmosphere can be air or nitrogen.
  • the storage temperature can be a known temperature, for example, room temperature (20 ° C. to 25 ° C.), refrigeration temperature (0 ° C. to 5 ° C.), and freezing temperature ( ⁇ 50 ° C. to ⁇ 10 ° C.). .
  • the storage temperature is preferably a freezing temperature or a refrigeration temperature from the viewpoint of preventing unexpected deterioration of the transfer film.
  • the storage temperature includes 5 ° C., ⁇ 10 ° C., ⁇ 20 ° C., and ⁇ 30 ° C.
  • the storage period is not particularly limited, and examples thereof include an embodiment in which the transfer film is manufactured and stored at 5 ° C. for 20 days after use, and an embodiment in which the transfer film is stored at ⁇ 20 ° C. for 50 days.
  • the laminate of the present disclosure includes a transparent substrate and the above-described transfer film of the present disclosure laminated on the transparent substrate, and may further include another layer as necessary.
  • the transparent substrate is a substrate having transparency, and is preferably a material having no optical distortion and high transparency.
  • the term “transparent” in the present disclosure means that the transmittance of all visible light is 85% or more, and is preferably 90% or more, and more preferably 95% or more.
  • a glass substrate or a resin substrate is preferable.
  • a resin base material is preferable because it is lightweight and hard to break.
  • the resin substrate include a transparent substrate made of a resin such as polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate (PC), triacetyl cellulose (TAC), and cycloolefin polymer (COP).
  • the transparent substrate preferably has a refractive index of 1.6 to 1.78 and a thickness of 50 ⁇ m to 200 ⁇ m.
  • the transparent substrate may have a single-layer structure or a laminate structure of two or more layers.
  • the refractive index means the refractive index of all layers of the transparent substrate.
  • the thickness of the transparent base material means the total thickness of all the layers.
  • the transparent substrate a substrate having a conductive member (for example, an electrode or a wiring) on at least one surface is preferable, and a substrate having at least one of an electrode and a wiring on both surfaces is more preferable.
  • the transparent substrate is preferably a substrate having at least one of a touch panel electrode and a touch panel wiring.
  • a transparent conductive material and a metal material are preferable.
  • a transparent conductive material for example, a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide) is preferable.
  • the metal material include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements.
  • examples of the touch panel electrode include a transparent electrode pattern disposed at least in an image display area of the touch panel.
  • the touch panel electrode may extend from the image display area to the frame of the touch panel.
  • the wiring for the touch panel for example, a drawing wiring (extraction wiring) arranged in a frame portion of the touch panel is cited, and a metal material is preferable.
  • a material of the routing wiring copper, molybdenum, aluminum or titanium is preferable, and copper is particularly preferable.
  • the laminate of the present disclosure has the above-described first photosensitive layer on one side of the transparent substrate, and the other side of the transparent substrate (that is, the transfer film of the present disclosure of the transparent substrate is laminated thereon). It is preferable to further include a second photosensitive layer on the side opposite to the opposite side).
  • a resist pattern preferably a resist pattern having a different pattern from each other
  • fine patterns can be formed on both sides of the transparent substrate.
  • Wiring patterns preferably, wiring patterns having different patterns from each other
  • the second photosensitive layer may be the same layer as the above-described first photosensitive layer, or may be different layers.
  • the second photosensitive layer is preferably a layer having the same component composition as the first photosensitive layer.
  • a first photosensitive layer is provided on one side of the transparent substrate, and a second photosensitive layer is provided on the other side, and it is possible to simultaneously irradiate light using the same light source.
  • the first photosensitive layer and the second photosensitive layer may be irradiated using different light sources, and the wavelengths of the irradiated light may be different.
  • the second photosensitive layer can be a layer containing at least a binder polymer, a polymerizable compound, and a photopolymerization initiator, and further contains other components such as a surfactant, a solvent, and an additive, if necessary. May be. Details and preferred embodiments of other components such as a binder polymer, a polymerizable compound, a photopolymerization initiator, a surfactant, a solvent, and an additive in the second photosensitive layer are the same as those in the first photosensitive layer.
  • the second photosensitive layer preferably contains a binder polymer, a polymerizable compound, and a photopolymerization initiator.
  • the thickness of the second photosensitive layer is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and particularly preferably 12 ⁇ m or less.
  • the thickness of the second photosensitive layer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and particularly preferably 3 ⁇ m or more from the viewpoint of production suitability.
  • the method for forming the second photosensitive layer is not particularly limited, and a known method can be used.
  • the second photosensitive layer is formed, for example, by applying a coating solution for forming the second photosensitive layer (coating solution for the second photosensitive layer) on a transparent substrate, or by applying the above-described book on the transparent substrate. It can be formed by a method of attaching a transfer material different from the disclosed transfer film.
  • a transfer film having a temporary support and a second photosensitive layer formed by applying and drying a coating solution for the second photosensitive layer on the temporary support can be used,
  • a transfer film having another layer (for example, the above-described intermediate layer) between the temporary support and the second photosensitive layer may be used.
  • the method of applying and drying the coating solution for the second photosensitive layer is the same as in the case of the first photosensitive layer described above, and a known method can be applied. And the same method as the method used for coating and drying.
  • the pattern forming method of the present disclosure includes a step of laminating the above-described transfer film of the present disclosure on one side of a transparent substrate (hereinafter, a laminating step), and a binder polymer on the other side of the transparent substrate.
  • Patterning step a step of forming different patterns on both sides of the transparent substrate by developing both sides of the transparent substrate after the irradiation is performed. Further, the pattern forming method of the present disclosure may further include another step as necessary.
  • the above-described transfer film of the present disclosure is bonded to one side of the transparent substrate.
  • the transfer film of the present disclosure can be attached to one side of the transparent substrate (for example, the side on which the electrodes and the like are arranged) by, for example, laminating.
  • Lamination can be performed using a known laminator such as a vacuum laminator and an auto-cut laminator.
  • the lamination temperature is preferably from 80 ° C to 150 ° C, more preferably from 90 ° C to 150 ° C, and particularly preferably from 100 ° C to 150 ° C.
  • the lamination temperature refers to a surface temperature of a roll of a laminator provided with the roll (hereinafter, roll temperature).
  • the temperature of the transparent substrate during lamination is not particularly limited.
  • the temperature of the transparent substrate during lamination is preferably from 10 ° C to 150 ° C, more preferably from 20 ° C to 150 ° C, even more preferably from 30 ° C to 150 ° C.
  • the linear pressure during lamination is preferably 0.5 MPa to 10 MPa, more preferably 0.5 MPa to 5 MPa, and particularly preferably 0.5 MPa to 1 MPa.
  • the transport speed (lamination speed) during lamination is preferably from 0.5 m / min to 5 m / min, more preferably from 1.5 m / min to 3 m / min.
  • the protective film is peeled off from the transfer film to expose the light-shielding layer.
  • the transfer film and the transparent substrate are bonded together such that the exposed light-shielding layer is in contact with the surface of the transparent substrate on which the electrodes and the like are arranged.
  • the light-shielding layer of the transfer film is brought into close contact with the transparent substrate, and a laminate having a laminated structure of temporary support / first photosensitive layer / intermediate layer / light-shielding layer / electrode / transparent substrate is formed.
  • the electrodes and the like are a part of the transparent substrate, and are used, for example, as a substrate for a touch panel. Thereafter, if necessary, the temporary support is peeled from the laminate.
  • a second photosensitive layer containing a binder polymer, a polymerizable compound, and a photopolymerization initiator is formed on the other side of the transparent substrate, that is, on a side having no first photosensitive layer and no light-shielding layer. I do.
  • the formation of the second photosensitive layer is performed, for example, by applying a coating solution for forming the second photosensitive layer (a coating solution for the second photosensitive layer) on a transparent base material, or by using a transparent base material.
  • the transfer film may be formed by any of the above-described methods of attaching a transfer material different from the transfer film of the present disclosure.
  • a known method can be applied in the same manner as in the formation of the first photosensitive layer described above.
  • the same method as the method used for drying may be mentioned.
  • the method of bonding the transfer material can be performed in the same manner as in the bonding step described above.
  • Light irradiation step In the light irradiation step, light is irradiated on both sides of the transparent substrate in different patterns. That is, in this step, pattern exposure is performed in such a manner that there is an exposed portion and a non-exposed portion. In this step, the light irradiated from the side on which the first photosensitive layer is disposed with respect to the transparent base material cures the exposed portion of the first photosensitive layer that has been subjected to pattern exposure, and finally becomes a cured film .
  • the pattern-exposed exposed portion of the second photosensitive layer is cured by the light irradiated from the side on which the second photosensitive layer is disposed with respect to the transparent base material, and finally, Becomes a cured film.
  • the non-exposed portions in the pattern exposure are not cured, and are removed (dissolved) by a developer in the next patterning step.
  • the non-exposed portion may form an opening of the cured film after the developing step.
  • the pattern exposure may be exposure through a mask or digital exposure using a laser or the like.
  • any light source that can irradiate light for example, 365 nm or 405 nm
  • the light source include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps.
  • Exposure is preferably 5mJ / cm 2 ⁇ 200mJ / cm 2, more preferably 10mJ / cm 2 ⁇ 200mJ / cm 2.
  • pattern exposure may be performed before the temporary support is peeled off, and then the temporary support may be peeled off. After exfoliating the body, pattern exposure may be performed.
  • the first photosensitive layer and the second photosensitive layer may be subjected to a heat treatment (so-called PEB (Post Exposure Bake)) after the pattern exposure and before the patterning step (that is, before the development). Good.
  • PEB Post Exposure Bake
  • Patterning process different patterns are formed on both sides of the transparent base material by developing both sides of the transparent base material after the light irradiation is performed in the light irradiation step.
  • the developer is not particularly limited, and a known developer such as a developer described in JP-A-5-72724 can be used.
  • the developing solution is preferably a developing solution capable of dissolving the unexposed photosensitive resin layer.
  • a compound having a pKa of 7 to 13 eg, sodium carbonate, potassium hydroxide, etc.
  • a developer containing a concentration of L is preferred. More specifically, an aqueous solution of sodium carbonate, an aqueous solution of potassium hydroxide and the like can be mentioned.
  • a small amount of an organic solvent miscible with water may be added to the developer.
  • water-miscible organic solvents include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ⁇ -caprolactone, ⁇ -butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ⁇ -caprolactam, N-methylpyrrolidone, and the like.
  • the concentration of the organic solvent is preferably from 0.1% by mass to 30% by mass.
  • a known surfactant can be further added to the developer.
  • the concentration of the surfactant is preferably 0.01% by mass to 10% by mass.
  • any method such as paddle development, shower development, a combination of shower development and spin development, and dip development may be used.
  • shower development a developer is sprayed on the exposed first and second photosensitive layers by a shower to remove uncured portions, whereby a patterned cured product can be formed. After the development, it is preferable to remove a development residue while spraying a detergent or the like with a shower and rubbing with a brush or the like.
  • the temperature of the developer is preferably from 20 ° C. to 40 ° C.
  • the pH of the developer is preferably from 8 to 13.
  • the transfer film 41 of the present disclosure is attached to one side of the transparent substrate 21 (attaching step), and the transfer film 41 of the present disclosure is further attached to the other side of the transparent substrate 21.
  • a transfer film 43 different from the film 41 is attached (second photosensitive layer forming step), and a laminate having a laminate structure shown in FIG. 3 is prepared, for example.
  • the first photomask 31 is disposed on the side of the laminate including the transfer film 41, and the first photomask 31 is disposed on the side of the laminate including the transfer film 43.
  • a second photomask 33 having a different pattern from that of the photomask 31 is arranged, and light is irradiated from both sides of the stacked body via the respective photomasks (light irradiation step).
  • different pattern exposures are performed on the first photosensitive layer 17 and the second photosensitive layer 27, respectively.
  • the first photomask 31 and the second photomask 33 are removed, and the temporary supports 19 and 19a disposed on both sides of the stacked body are respectively peeled off.
  • the first photosensitive layer 17 and the second photosensitive layer 27 exposed on both sides of the laminate are subjected to a developing process (patterning step).
  • the pattern forming method of the present disclosure is suitably used for forming at least one of an electrode for a touch panel and a wiring for a touch panel.
  • Example 1 ⁇ Preparation of transfer film A> A first photosensitive layer forming composition B-1 having the following composition was coated on a temporary support (Lumilar (registered trademark) 16QS62 (thickness: 16 ⁇ m), Toray Industries, Inc .; polyethylene terephthalate film) using a slit nozzle. It was dried with hot air at 100 ° C. for 2 minutes to form a first photosensitive layer having a dry thickness of 6 ⁇ m.
  • a temporary support Liilar (registered trademark) 16QS62 (thickness: 16 ⁇ m), Toray Industries, Inc .; polyethylene terephthalate film
  • Table 1 “Polymer” refers to a binder polymer according to the present disclosure
  • radical polymerizable compound” refers to a polymerizable compound according to the present disclosure.
  • the ratio of each structural unit in the polymer A-1 and Acrybase FF187 is a molar ratio.
  • Me represents a methyl group.
  • a composition C-1 for forming an intermediate layer having the following composition was applied using a slit-shaped nozzle, and dried with hot air at 100 ° C. for 2 minutes to form an intermediate layer having a dry thickness of 1 ⁇ m. Formed.
  • composition A-1 for forming a light-shielding layer having the composition shown in Table 3 below was applied to the intermediate layer using a slit-shaped nozzle, and dried with hot air at 100 ° C. for 2 minutes to form a light-shielding layer having a dry thickness of 3 ⁇ m. A layer was formed.
  • a protective film (Trefane (registered trademark) 12KW37 (thickness: 12 ⁇ m), Toray Industries, Inc .; polypropylene film) is laminated on the light-shielding layer, and the temporary support / first photosensitive layer / intermediate layer / light-shielding layer / protective film A transfer film A having a laminated structure of was prepared.
  • a laminate was produced as follows.
  • the protective film of the film piece was peeled off.
  • the film piece is placed on one side of the COP substrate such that the surface of the light-shielding layer exposed by peeling of the protective film is in contact with the cycloolefin resin film substrate (thickness: 50 ⁇ m; hereinafter, also referred to as “COP substrate”).
  • laminated under the following conditions laminated under the following conditions (lamination step).
  • ⁇ Lamination conditions> ⁇ Roll temperature: 110 ° C ⁇ Line pressure: 0.6MPa ⁇ Linear speed (lamination speed): 2.0 m / min
  • the residue of the first photosensitive layer indicates that the first photosensitive layer or the light-shielding layer has been cured by irradiation light from the second photosensitive layer side (that is, exposure fog has occurred).
  • the residue of the first photosensitive layer the residue of the first photosensitive layer remaining on the surface of the light-shielding layer was confirmed, and the area ratio occupied in the unirradiated region, which is the observation region, was determined.
  • the light-shielding effect of the light-shielding layer is low, the first photosensitive layer is exposed to irradiation light from the second photosensitive layer side, and a residue is easily generated.
  • the residue of the light-shielding layer As for the residue of the light-shielding layer, the residue of the light-shielding layer remaining on the surface of the transparent substrate was confirmed, and the area ratio occupied in the unirradiated region, which is the observation region, was determined. Even if the light-blocking effect of the light-blocking layer is ensured, if the light-blocking layer itself has photosensitivity, the light-blocking layer itself is exposed to light and residues are likely to be generated. ⁇ Evaluation criteria> A: No residue is observed. B: Residue can be confirmed, and the area ratio of the residue is 5% or less with respect to the area of the unirradiated region.
  • C Residue was confirmed, and the area ratio of the residue was more than 5% and 10% or less based on the area of the unirradiated region.
  • D Residue can be confirmed, and the area ratio of the residue is more than 10% and 30% or less with respect to the area of the unirradiated region.
  • E Residue was confirmed, and the area ratio of the residue exceeded 30% of the area of the unirradiated region.
  • Optical density (OD) of light shielding layer A composition A-1 for forming a light-shielding layer is applied on a temporary support (Lumirror 16QS62; thickness 16 ⁇ m) using a slit-shaped nozzle, and dried in a convection oven at a temperature of 100 ° C. for 2 minutes to form a light-shielding layer having a thickness of 3 ⁇ m.
  • a protective film Terefane 12KW37 was further stuck on the light-shielding layer to prepare a transfer film having a laminated structure of temporary support / light-shielding layer / protective film.
  • This transfer film was cut into a size of 5 cm x 5 cm to form a film piece for measurement, and the protective film was peeled off from the film piece for measurement. Then, the film piece for measurement is superimposed on the glass so that the surface of the light-shielding layer exposed by peeling of the protective film is in contact with the glass substrate, and the glass substrate (Eagle XG (thickness 0.7 mm)) is formed under the same conditions as above. (Manufactured by Corning Incorporated)) to obtain a laminate having a laminated structure of temporary support / light-shielding layer / glass substrate.
  • the optical density of the light-shielding layer of this laminate was measured using a transmission densitometer (BMT-1, manufactured by Sakata Inx Engineering). Further, the optical densities of the temporary support and the glass substrate used for producing the laminate were measured in the same manner as described above. Then, the optical density of the temporary support and the glass substrate was subtracted from the optical density of the laminate to obtain the optical density of the light-shielding layer. The measurement results are shown in Table 3 below.
  • Example 1 was repeated in the same manner as in Example 1 except that the composition A-1 for forming a light-shielding layer was changed to the compositions A-2 to A-4 or AA-1 for forming a light-shielding layer shown in Table 3. Then, a transfer film was prepared and the same measurement and evaluation were performed. The results of the measurement and evaluation are shown in Table 3 below.
  • Example 3 As shown in Table 3, in Examples 1 to 4 using the transfer film of the present disclosure, a light-shielding effect was obtained by providing a light-shielding layer having a constant optical density. Even if it was performed, one side was hardly affected by the irradiation light on the other side, and a fine pattern could be formed on both sides of the transparent substrate. Among them, in Example 3, since the light-shielding layer contained a photopolymerization initiator, the first photosensitive layer was not exposed due to the light-shielding effect of the light-shielding layer and the residue was suppressed to a small extent, but the polymerization reaction of the light-shielding layer was slight.
  • Example 5 A transfer film was obtained in the same manner as in Example 1 except that the composition C-1 for forming an intermediate layer in Example 1 was changed to the compositions C-2 or C-3 for forming an intermediate layer shown in Table 4. Was prepared, and similar measurements and evaluations were performed. The results of the measurement and evaluation are shown in Table 5 below.

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Abstract

Provided is a transfer film which has, in the following order: a temporary support; a first photosensitive layer including a binder polymer, a polymerizable compound, and a photopolymerization initiator; and a light-shielding layer including at least a binder polymer and having an optical density of 0.5 or more. Also provided are a laminate and a pattern forming method.

Description

転写フィルム、積層体、及びパターン形成方法Transfer film, laminate, and pattern forming method
　本開示は、転写フィルム、積層体、及びパターン形成方法に関する。 The present disclosure relates to a transfer film, a laminate, and a pattern forming method.
　近年、携帯電話、カーナビゲーション、パーソナルコンピュータ、券売機、銀行の端末などの電子機器では、液晶装置などの表面にタブレット型の入力装置が配置される。液晶装置の画像表示領域に表示された指示画像を参照しながら、指示画像が表示されている箇所に指又はタッチペンなどを触れることで、指示画像に対応する情報の入力が行える装置がある。
　入力装置（以下、タッチパネルともいう。）には、抵抗膜型、静電容量型などがある。静電容量型の入力装置の場合には、単に一枚の基板に透光性導電膜を形成すればよいという利点がある。 2. Description of the Related Art In recent years, in electronic devices such as a mobile phone, a car navigation system, a personal computer, a ticket vending machine, and a bank terminal, a tablet-type input device is arranged on a surface of a liquid crystal device or the like. There is a device that can input information corresponding to an instruction image by touching a position where the instruction image is displayed with a finger or a touch pen while referring to an instruction image displayed in an image display area of a liquid crystal device.
Examples of the input device (hereinafter, also referred to as a touch panel) include a resistive film type and a capacitance type. In the case of a capacitance-type input device, there is an advantage that a light-transmitting conductive film may be simply formed on one substrate.
　導電膜がパターン状に形成された配線基板としては、金属配線パターンが基板の両側に配設された両面プリント配線基板が用いられる傾向にある。
　基板上に金属配線が配設された配線基板は、基板に形成された金属膜の上にフォトレジスト法によりパターン状のレジスト膜を形成し、レジスト膜をマスクとして金属膜をエッチング等することで作製することができる。そして、両面プリント配線基板の場合には、パターン状のレジスト膜をマスクとしてエッチングする作業を基板の両側に対して行うことになる。 As a wiring board on which a conductive film is formed in a pattern, there is a tendency to use a double-sided printed wiring board in which a metal wiring pattern is disposed on both sides of the board.
A wiring board in which metal wiring is provided on a substrate is formed by forming a patterned resist film by a photoresist method on a metal film formed on the substrate and etching the metal film using the resist film as a mask. Can be made. In the case of a double-sided printed wiring board, an operation of etching using a patterned resist film as a mask is performed on both sides of the board.
　上記に関連する技術として、透明基材の両面にパターニングする方法に関する開示がある（例えば、特開２０１１－１５４０８０号公報参照）。具体的には、透明基材の表裏両面に設けられた透明金属膜のパターン形成において、透明金属膜の少なくとも一方の透明金属膜上に露光光を遮光する不透明層を形成し、透明基材の表裏両面にフォトレジストを塗布してフォトレジスト膜を形成し、フォトレジスト膜を有する両面に異なるパターン露光を行って、それぞれレジストパターンを形成し得ることが記載されている。 技術 As a technique related to the above, there is a disclosure related to a method of patterning both surfaces of a transparent substrate (for example, see Japanese Patent Application Laid-Open No. 2011-154080). Specifically, in forming the pattern of the transparent metal film provided on both the front and back surfaces of the transparent substrate, an opaque layer that blocks exposure light is formed on at least one of the transparent metal films, It is described that a photoresist film is formed by applying a photoresist on both front and back surfaces, and different pattern exposures can be performed on both surfaces having the photoresist film to form respective resist patterns.
　また、プリント配線基板の製造に有用な材料として、支持体上に、バインダー、重合性化合物及び光重合開始剤を含む第一感光層と、第一感光層の光感度よりも相対的に高い光感度を示す第二感光層とがこの順に積層された感光性転写シートが開示されている（例えば、特開２００５－３３１６９５号公報参照）。 Further, as a material useful for the manufacture of a printed wiring board, on a support, a first photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator, and a light having a relatively higher light sensitivity than the first photosensitive layer. A photosensitive transfer sheet in which a second photosensitive layer exhibiting sensitivity is laminated in this order is disclosed (for example, see JP-A-2005-331695).
　上記のように、透明基材の両側にそれぞれ配線パターンを形成することについては、従来から行われている。しかし、透明基材の両側に感光性のレジストパターンを設けてそれぞれ露光し、例えば透明基材の両側に互いに異なるパターンを形成しようとすると、透明基材の一方の側から照射された光が透明基材を透過して他方の側に到達しやすい。そのため、光が照射される一方の側では良好なパターンが形成できても、他方の側では、透過した光の影響を受けてパターンの形状を著しく損なう場合がある。
  As described above, formation of wiring patterns on both sides of a transparent substrate has been conventionally performed. However, when a photosensitive resist pattern is provided on both sides of the transparent base material and exposed to light, for example, when trying to form different patterns on both sides of the transparent base material, light irradiated from one side of the transparent base material becomes transparent. It easily passes through the base material and reaches the other side. Therefore, even if a good pattern can be formed on one side irradiated with light, the shape of the pattern may be significantly impaired on the other side under the influence of transmitted light.
　従来技術のうち、上記した特開２０１１－１５４０８０号公報では、不透明層を設けて一方の側に照射された光が他方の側へ透過することが防止される。しかし、不透明層にはアルミニウム等の金属が用いられるため、レジストパターンを形成した後に配線パターンをエッチング形成する際には、金属配線を形成するためのエッチングとは別にあらかじめ不透明層をエッチングする作業を設けなければならず、工程数が多くなる課題がある。また、不透明層がフォトレジストの現像処理の際に除去されないために、現像後そのまま透明基材の両方の側を同時にエッチング処理することも不可能である。
　しかも、特開２０１１－１５４０８０号公報に記載の技術では、パターン露光時の光が不透明層で反射しやすいため、反射光がパターン精度を損ない、パターンの精細さを損ないやすい傾向がある。 Among the prior arts, in the above-described Japanese Patent Application Laid-Open No. 2011-154080, an opaque layer is provided to prevent light irradiated on one side from transmitting to the other side. However, since metal such as aluminum is used for the opaque layer, when forming a wiring pattern by etching after forming a resist pattern, it is necessary to perform an operation of etching the opaque layer in advance separately from the etching for forming the metal wiring. However, there is a problem that the number of steps increases. Also, since the opaque layer is not removed during the development of the photoresist, it is impossible to simultaneously etch both sides of the transparent substrate as it is after development.
In addition, in the technique described in Japanese Patent Application Laid-Open No. 2011-154080, light at the time of pattern exposure is easily reflected by the opaque layer.
　本開示は、上記に鑑みなされたものである。
　本発明の一実施形態が解決しようとする課題は、転写後のパターン露光時の、透明基材の一方の側からの照射光に起因した他方の側のパターン形成性への影響が抑えられ、簡易に精細なパターンを形成することができる転写フィルム又は積層体を提供することにある。
　本発明の他の一実施形態が解決しようとする課題は、転写後のパターン露光時の、透明基材の一方の側からの照射光に起因した他方の側のパターン形成性への影響を抑えつつ、簡易に精細なパターンを形成することができるパターン形成方法を提供することにある。 The present disclosure has been made in view of the above.
The problem to be solved by one embodiment of the present invention is that during pattern exposure after transfer, the influence on pattern formability on the other side due to irradiation light from one side of the transparent substrate is suppressed, An object of the present invention is to provide a transfer film or a laminate that can easily form a fine pattern.
The problem to be solved by another embodiment of the present invention is to suppress the influence on the pattern formability on the other side due to irradiation light from one side of the transparent substrate during pattern exposure after transfer. Another object of the present invention is to provide a pattern forming method capable of easily forming a fine pattern.
　課題を解決するための具体的手段には、以下の態様が含まれる。
　＜１＞　仮支持体と、バインダーポリマー、重合性化合物、及び光重合開始剤を含む第１感光層と、少なくともバインダーポリマーを含み、かつ、光学濃度が０．５以上である遮光層と、をこの順に有する転写フィルムである。
　＜２＞　遮光層が、更に、紫外線吸収材料を含む＜１＞に記載の転写フィルムである。
　＜３＞　紫外線吸収材料が、カーボンブラックを含む＜２＞に記載の転写フィルムである。
　＜４＞　遮光層が、更に、重合性化合物を含む＜１＞～＜３＞のいずれか１つに記載の転写フィルムである。
　＜５＞　光重合開始剤の含有量が、遮光層の全固形分量に対して、１質量％以下である＜１＞～＜４＞のいずれか１つに記載の転写フィルムである。
　＜６＞　第１感光層と遮光層との間に、中間層を有する＜１＞～＜５＞のいずれか１つに記載の転写フィルムである。　
　＜７＞　中間層が、水又は炭素数１～４の低級アルコールに対して可溶性を有するバインダーポリマーを含む＜６＞に記載の転写フィルムである。
　＜８＞　中間層が、更に、重合性化合物及び光重合開始剤を含む＜６＞又は＜７＞に記載の転写フィルムである。
　＜９＞　透明基材と、＜１＞～＜８＞のいずれか１つに記載の転写フィルムと、を有する積層体である。
　＜１０＞　透明基材の、転写フィルムが積層された側と反対側に、第２感光層を有する＜９＞に記載の積層体である。
　＜１１＞　第２感光層が、バインダーポリマー、重合性化合物、及び光重合開始剤を含有する＜１０＞に記載の積層体である。 Specific means for solving the problems include the following aspects.
<1> A temporary support, a first photosensitive layer containing a binder polymer, a polymerizable compound, and a photopolymerization initiator, and a light-shielding layer containing at least a binder polymer and having an optical density of 0.5 or more. It is a transfer film having this order.
<2> The transfer film according to <1>, wherein the light-shielding layer further contains an ultraviolet absorbing material.
<3> The transfer film according to <2>, wherein the ultraviolet absorbing material contains carbon black.
<4> The transfer film according to any one of <1> to <3>, wherein the light-shielding layer further contains a polymerizable compound.
<5> The transfer film according to any one of <1> to <4>, wherein the content of the photopolymerization initiator is 1% by mass or less based on the total solid content of the light-shielding layer.
<6> The transfer film according to any one of <1> to <5>, including an intermediate layer between the first photosensitive layer and the light-shielding layer.
<7> The transfer film according to <6>, wherein the intermediate layer contains a binder polymer having solubility in water or a lower alcohol having 1 to 4 carbon atoms.
<8> The transfer film according to <6> or <7>, wherein the intermediate layer further contains a polymerizable compound and a photopolymerization initiator.
<9> A laminate including a transparent base material and the transfer film according to any one of <1> to <8>.
<10> The laminate according to <9>, wherein the transparent substrate has a second photosensitive layer on a side opposite to a side on which the transfer film is laminated.
<11> The laminate according to <10>, wherein the second photosensitive layer contains a binder polymer, a polymerizable compound, and a photopolymerization initiator.
　＜１２＞　透明基材の一方の側に、＜１＞～＜８＞のいずれか１つに記載の転写フィルムを貼り合わせる工程と、透明基材の他方の側に、バインダーポリマー、重合性化合物、及び光重合開始剤を含む第２感光層を形成する工程と、透明基材の両方の側に対して、光をそれぞれ異なるパターンにて照射する工程と、照射が行われた後の透明基材の両方の側を現像処理することで、透明基材の両方の側にそれぞれ異なるパターンを形成する工程と、を有するパターン形成方法である。
　＜１３＞　透明基材は、両方の面に金属電極及び金属配線の少なくとも一方を有する＜１２＞に記載のパターン形成方法である。
　＜１４＞　タッチパネル用電極及びタッチパネル用配線の少なくとも一方の形成に用いられる＜１２＞又は＜１３＞に記載のパターン形成方法である。 <12> a step of attaching the transfer film according to any one of <1> to <8> to one side of the transparent substrate, and a binder polymer and a polymerizable compound on the other side of the transparent substrate. Forming a second photosensitive layer containing a photoinitiator, and irradiating both sides of the transparent substrate with light in different patterns, respectively. Forming different patterns on both sides of the transparent substrate by developing both sides of the material.
<13> The pattern forming method according to <12>, wherein the transparent substrate has at least one of a metal electrode and a metal wiring on both surfaces.
<14> The pattern forming method according to <12> or <13>, which is used for forming at least one of a touch panel electrode and a touch panel wiring.
　本発明の一実施形態によれば、転写後のパターン露光時の、透明基材の一方の側からの照射光に起因した他方の側のパターン形成性への影響が抑えられ、簡易に精細なパターンを形成することができる転写フィルム又は積層体が提供される。
　本発明の他の一実施形態によれば、転写後のパターン露光時の、透明基材の一方の側からの照射光に起因した他方の側のパターン形成性への影響を抑えつつ、簡易に精細なパターンを形成することができるパターン形成方法が提供される。 According to an embodiment of the present invention, at the time of pattern exposure after transfer, the influence on the pattern formability on the other side due to the irradiation light from one side of the transparent substrate is suppressed, and the fine pattern is easily formed. A transfer film or laminate capable of forming a pattern is provided.
According to another embodiment of the present invention, at the time of pattern exposure after transfer, while suppressing the effect on the pattern formability of the other side due to irradiation light from one side of the transparent substrate, easily A pattern forming method capable of forming a fine pattern is provided.
図１は、本開示の転写フィルムの一実施形態を示す断面構成図である。FIG. 1 is a cross-sectional configuration diagram illustrating an embodiment of the transfer film of the present disclosure. 図２は、本開示の積層体の一実施形態を示す断面構成図である。FIG. 2 is a cross-sectional configuration diagram illustrating an embodiment of the laminate of the present disclosure. 図３は、本開示の積層体の他の一実施形態を示す断面構成図である。FIG. 3 is a cross-sectional configuration diagram illustrating another embodiment of the laminate of the present disclosure. 図４は、本開示のパターン形成方法により透明基材の両側に互いに異なるパターンを同時に形成するところを説明するための工程図である。FIG. 4 is a process diagram for explaining that different patterns are simultaneously formed on both sides of a transparent substrate by the pattern forming method of the present disclosure.
　以下、本開示の内容について詳細に説明する。
　以下に記載する構成要件の説明は、本開示の代表的な実施態様に基づいてなされることがあるが、本開示はそのような実施態様に限定されるものではない。 Hereinafter, the contents of the present disclosure will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.
　本開示において、数値範囲を示す「～」とはそ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意味で使用される。
　本開示において段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。 In the present disclosure, “to” indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit and the upper limit.
In the numerical ranges described in stages in the present disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described in stages. Further, in the numerical range described in the present disclosure, the upper limit or the lower limit of the numerical range may be replaced with the value shown in the embodiment.
　本開示における基（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。
　また、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。
　更に、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。
　本開示において、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上記複数の物質の合計量を意味する。 In the notation of a group (atomic group) in the present disclosure, the notation of not indicating substituted or unsubstituted includes not only one having no substituent but also one 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 the present disclosure, “mass%” and “weight%” have the same meaning, and “mass part” and “part by weight” have the same meaning.
Furthermore, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
In the present disclosure, the amount of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, means the total amount of the plurality of substances present in the composition I do.
　本開示において、「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。 に お い て In the present disclosure, the term “step” is included in this term as long as the intended purpose of the step is achieved not only in an independent step but also in cases where it cannot be clearly distinguished from other steps.
　本開示において、「（メタ）アクリル酸」は、アクリル酸及びメタクリル酸の両方を包含する概念であり、「（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両方を包含する概念であり、「（メタ）アクリロイル基」は、アクリロイル基及びメタクリロイル基の両方を包含する概念である。 In the present disclosure, “(meth) acrylic acid” is a concept including both acrylic acid and methacrylic acid, “(meth) acrylate” is a concept including both acrylate and methacrylate, and “(meth) acrylate” ) "Acryloyl group" is a concept encompassing both acryloyl and methacryloyl groups.
　本開示において、樹脂中の構成単位の割合は、特に断りが無い限り、質量割合を表す。
　本開示において、分子量分布がある場合の分子量は、特に断りが無い限り、重量平均分子量（Ｍｗ）を表す。 In the present disclosure, the ratio of a structural unit in a resin represents a mass ratio unless otherwise specified.
In the present disclosure, the molecular weight when there is a molecular weight distribution represents a weight average molecular weight (Mw), unless otherwise specified.
　以下、本開示の転写フィルム、並びに、本開示の転写フィルムを用いた積層体及びパターン形成方法について、詳細に説明する。 Hereinafter, the transfer film of the present disclosure, and a laminate and a pattern forming method using the transfer film of the present disclosure will be described in detail.
＜転写フィルム＞
　本開示の転写フィルムは、仮支持体と、バインダーポリマー、重合性化合物、及び光重合開始剤を含む第１感光層と、少なくともバインダーポリマーを含み、かつ、光学濃度が０．５以上である遮光層と、をこの順に有し、必要に応じて、更に、中間層等の他の層を有してもよい。 <Transfer film>
The transfer film of the present disclosure includes a temporary support, a first photosensitive layer containing a binder polymer, a polymerizable compound, and a photopolymerization initiator, and a light-shielding film containing at least a binder polymer and having an optical density of 0.5 or more. And in this order, and if necessary, may further have another layer such as an intermediate layer.
　従来から、フォトレジスト法により形成したレジストパターンをマスクとしてエッチング法により配線パターン等を形成する技術は知られている。レジスト材料の一例として感光性転写フィルムを用いる方法も広く用いられている。
　そして近年では、透明基材の両側に感光性の樹脂組成物を設けてそれぞれ露光し、例えば透明基材の両側に互いに異なるパターンを形成する技術が知られている。透明基材の両側からそれぞれ光照射した場合、透明基材の一方の側から照射された光は、透明基材を透過して他方の側にまで到達する傾向がある。そのため、光照射が行われる一方の側では良好なパターンが形成されても、他方の側では、一方の側から透過した光の影響を受けて潜像が乱れ、現像後に形成されるパターンの形状を著しく損なう場合がある。 2. Description of the Related Art Conventionally, a technique for forming a wiring pattern or the like by an etching method using a resist pattern formed by a photoresist method as a mask is known. A method using a photosensitive transfer film as an example of a resist material is also widely used.
In recent years, a technique has been known in which a photosensitive resin composition is provided on both sides of a transparent base material and exposed to light to form different patterns on both sides of the transparent base material, for example. When light is irradiated from both sides of the transparent substrate, light emitted from one side of the transparent substrate tends to pass through the transparent substrate and reach the other side. Therefore, even if a good pattern is formed on one side where light irradiation is performed, on the other side, the latent image is disturbed due to the influence of light transmitted from one side, and the shape of the pattern formed after development May be significantly impaired.
　特開２０１１－１５４０８０号公報に記載の技術のように、層間に不透明層を設けて、透明基材の一方の側に照射された光が他方の側へ透過しない層構造とされている場合には、透明基材の一方の側に照射された光の透過が防止され、他方の側の感光状態（潜像）を乱すことは生じにくい。ところが、特開２０１１－１５４０８０号公報に記載の技術は、不透明層にアルミニウム等の金属が用いられている。そのため、レジストパターンをマスクとしてエッチングにより配線パターンを形成する場合、配線パターンを形成するためのエッチング工程とは別にあらかじめ不透明層へのエッチング工程を設けなければならない。したがって、工程数が多く、コストの点でも不利である。
　しかも、特開２０１１－１５４０８０号公報に記載の発明のように、層間に配された不透明層が金属層である場合、金属層は多少なりとも光の反射を伴うため、パターン露光時の光が不透明層で反射して不要な露光効果が生じ、結果、パターンの精細さを損なう一因となる。
　また、不透明層は、光照射後の現像処理によってフォトレジストと同時に現像除去できないので、例えば透明基材の両方の側に形成されたフォトレジスト膜の現像時点では不透明層がそのまま残る。そのため、現像と同時にエッチング可能な状態を形成することができない。 As in the technique described in Japanese Patent Application Laid-Open No. 2011-154080, an opaque layer is provided between layers to form a layer structure in which light irradiated on one side of a transparent base material is not transmitted to the other side. In the case, the light irradiated on one side of the transparent substrate is prevented from being transmitted, and the photosensitive state (latent image) on the other side is hardly disturbed. However, in the technique described in JP-A-2011-154080, a metal such as aluminum is used for the opaque layer. Therefore, when a wiring pattern is formed by etching using a resist pattern as a mask, an etching step for the opaque layer must be provided in advance in addition to an etching step for forming the wiring pattern. Therefore, the number of steps is large, which is disadvantageous in terms of cost.
Moreover, when the opaque layer disposed between the layers is a metal layer as in the invention described in Japanese Patent Application Laid-Open No. 2011-154080, the metal layer involves reflection of light to some extent. Reflection from the opaque layer produces an unwanted exposure effect, which results in a loss of pattern definition.
Further, since the opaque layer cannot be developed and removed at the same time as the photoresist by the developing treatment after light irradiation, the opaque layer remains as it is at the time of development of the photoresist film formed on both sides of the transparent substrate, for example. Therefore, a state that can be etched simultaneously with the development cannot be formed.
　上記に鑑み、本開示の転写フィルムでは、仮支持体上に、バインダーポリマー、重合性化合物、及び光重合開始剤を含む第１感光層と、バインダーポリマーを含み、かつ、光学濃度が０．５以上である遮光層と、をこの順に積層した積層構造とする。これにより、例えば図２のように、透明基材２１の一方の側に転写フィルム４１を貼り合わせて透明基材２１／遮光層１３／第１感光層１７／仮支持体１９の積層構造を有する積層体とした場合、一方の側（例えば、積層体の仮支持体１９側）から照射された照射光は、遮光層１３で遮断されて他方の側（例えば、積層体の透明基材２１側）への透過が抑制され、かつ、他方の側からの光も同様に遮光層１３で遮断されて一方の側への透過が抑制される。そして、このような層構成では、第１感光層１７及び遮光層１３は、一方の側からの照射光により第１感光層１７が感光した領域以外の領域において、第１感光層１７だけでなく遮光層１３も良好に現像除去され、現像と同時にエッチング可能な状態が得られ、かつ、透明基材２１上への遮光層１３の残存も生じにくい。結果、透明基材２１上に精度の高いパターンが形成される。
　この点は、例えば図３に示すように、透明基材２１の一方の側に転写フィルム４１を貼り合わせ、かつ、他方の側に第２感光層２７を有する別の転写フィルム４３を貼り合わせることで、仮支持体１９／第１感光層１７／遮光層１３／透明基材２１／第２感光層２７／仮支持体１９ａの積層構造を有する積層体１０１とした場合により顕著に現れる。つまり、一方の側（例えば、積層体の仮支持体１９側）から照射された照射光は、遮光層１３で遮断されて他方の側（例えば、図３の積層体の仮支持体１９ａ側）への透過が抑制され、かつ、他方の側から照射された照射光も同様に遮光層１３で遮断されて一方の側（例えば、図３の積層体の仮支持体１９側）への透過が抑制される。そして、このような層構成では、第１感光層及び遮光層は、一方の側からの照射光により第１感光層が感光していない領域で第１感光層１７だけでなく遮光層１３も良好に現像除去され、現像と同時にエッチング可能な状態が得られる。また、透明基材２１上への遮光層１３の残存及び第２感光層の残存も生じにくいので、透明基材２１上には、残渣が少なく、精度の高いパターンが形成される。
　上記のように、本開示の転写フィルムでは、層間に配された遮光層は、照射光を吸収しやすく、照射された光の反射を生じにくいので、反射光に起因した不要な露光効果が抑制され、パターンの精細さがより高められる。また、本開示における遮光層は、第１感光層の現像の際に除去可能な層であるので、パターンを顕在化する現像の過程で除去され、エッチング可能な状態を形成できる。したがって、現像後そのまま両側のエッチング処理が可能となる。 In view of the above, in the transfer film of the present disclosure, the first photosensitive layer containing the binder polymer, the polymerizable compound, and the photopolymerization initiator, the binder polymer, and the optical density are 0.5 on the temporary support. The light shielding layer described above is laminated in this order to form a laminated structure. Thereby, for example, as shown in FIG. 2, the transfer film 41 is attached to one side of the transparent substrate 21 to have a laminated structure of the transparent substrate 21 / the light shielding layer 13 / the first photosensitive layer 17 / the temporary support 19. In the case of a laminate, the irradiation light irradiated from one side (for example, the side of the temporary support 19 of the laminate) is blocked by the light shielding layer 13 and the other side (for example, the side of the transparent substrate 21 of the laminate) ) Is suppressed, and light from the other side is similarly blocked by the light shielding layer 13, so that transmission to one side is suppressed. In such a layer configuration, the first photosensitive layer 17 and the light-shielding layer 13 are formed not only in the first photosensitive layer 17 but also in a region other than the region where the first photosensitive layer 17 is exposed by the irradiation light from one side. The light-shielding layer 13 is also favorably developed and removed, so that a state in which etching can be performed simultaneously with development is obtained, and the light-shielding layer 13 hardly remains on the transparent substrate 21. As a result, a highly accurate pattern is formed on the transparent substrate 21.
This is because, for example, as shown in FIG. 3, a transfer film 41 is bonded to one side of the transparent substrate 21 and another transfer film 43 having the second photosensitive layer 27 is bonded to the other side. This is more remarkable when the laminated body 101 has a laminated structure of the temporary support 19 / first photosensitive layer 17 / light shielding layer 13 / transparent substrate 21 / second photosensitive layer 27 / temporary support 19a. That is, the irradiation light irradiated from one side (for example, the temporary support 19 side of the laminate) is blocked by the light blocking layer 13 and the other side (for example, the temporary support 19a side of the laminate in FIG. 3). The transmission to the one side (for example, the side of the temporary support 19 of the laminated body in FIG. 3) is also blocked by the light-shielding layer 13 so that the irradiation light irradiated from the other side is also blocked. Be suppressed. In such a layer configuration, the first photosensitive layer and the light-shielding layer are good in not only the first photosensitive layer 17 but also the light-shielding layer 13 in a region where the first photosensitive layer is not exposed to light from one side. And a state that can be etched simultaneously with the development is obtained. In addition, since the light-shielding layer 13 and the second photosensitive layer do not easily remain on the transparent substrate 21, a highly accurate pattern with few residues is formed on the transparent substrate 21.
As described above, in the transfer film of the present disclosure, the light-shielding layer disposed between the layers easily absorbs irradiation light and hardly reflects the irradiation light, so that unnecessary exposure effects due to the reflected light are suppressed. This increases the definition of the pattern. In addition, since the light-shielding layer according to the present disclosure is a layer that can be removed during the development of the first photosensitive layer, it can be removed in the course of development that reveals the pattern, and can be etched. Therefore, both sides can be etched as they are after development.
（第１感光層）
　第１感光層は、仮支持体の上に配置された感光性を有するネガ型の層であり、少なくともバインダーポリマー、重合性化合物、及び光重合開始剤を含む。第１感光層は、必要に応じて、更に界面活性剤、溶剤、及び添加剤等の他の成分を含んでもよい。 (First photosensitive layer)
The first photosensitive layer is a photosensitive negative type layer disposed on a temporary support, and includes at least a binder polymer, a polymerizable compound, and a photopolymerization initiator. The first photosensitive layer may further contain other components such as a surfactant, a solvent, and an additive, if necessary.
－バインダーポリマー－
　第１感光層は、バインダーポリマーの少なくとも一種を含有する。
　バインダーポリマーは、アルカリ性溶媒との接触により溶解しうる樹脂（いわゆるアルカリ可溶性樹脂）であることが好ましい。
　バインダーポリマーの酸価は、特に制限はないが、現像性の観点から、６０ｍｇ／ＫＯＨ以上であることが好ましい。具体的に、バインダーポリマーは、酸価６０ｍｇＫＯＨ／ｇ以上のバインダーポリマーであることが好ましく、酸価６０ｍｇＫＯＨ／ｇ以上のアルカリ可溶性樹脂であることがより好ましく、酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基含有アクリル樹脂であることが特に好ましい。 -Binder polymer-
The first photosensitive layer contains at least one binder polymer.
The binder polymer is preferably a resin that can be dissolved by contact with an alkaline solvent (so-called alkali-soluble resin).
The acid value of the binder polymer is not particularly limited, but is preferably 60 mg / KOH or more from the viewpoint of developability. Specifically, the binder polymer is preferably a binder polymer having an acid value of 60 mg KOH / g or more, more preferably an alkali-soluble resin having an acid value of 60 mg KOH / g or more, and containing a carboxy group having an acid value of 60 mg KOH / g or more. An acrylic resin is particularly preferred.
　酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基含有アクリル樹脂（以下、特定重合体と称することがある。）としては、上記酸価の条件を満たす限りにおいて特に制限はなく、公知の樹脂から適宜選択して用いることができる。
　例えば、特開２０１１－９５７１６号公報の段落００２５に記載のポリマーのうちの酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基含有アクリル樹脂であるバインダーポリマー、特開２０１０－２３７５８９号公報の段落００３３～００５２に記載のポリマーのうちの酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基含有アクリル樹脂等が、本実施形態における特定重合体として好ましく用いることができる。
　ここで、（メタ）アクリル樹脂は、（メタ）アクリル酸に由来する構成単位及び（メタ）アクリル酸エステルに由来する構成単位の少なくとも一方を含む樹脂を指す。
　（メタ）アクリル樹脂中における（メタ）アクリル酸に由来する構成単位及び（メタ）アクリル酸エステルに由来する構成単位の合計割合は、３０モル％以上が好ましく、５０モル％以上がより好ましい。 The carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more (hereinafter, may be referred to as a specific polymer) is not particularly limited as long as it satisfies the above acid value conditions, and may be appropriately selected from known resins. Can be used.
For example, among the polymers described in paragraph 0025 of JP-A-2011-95716, a binder polymer which is a carboxy group-containing acrylic resin having an acid value of 60 mg KOH / g or more, described in paragraphs 0033 to 0052 of JP-A-2010-237589. Among these polymers, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used as the specific polymer in the present embodiment.
Here, the (meth) acrylic resin refers to a resin containing at least one of a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylate.
The total ratio of the structural units derived from (meth) acrylic acid and the structural units derived from (meth) acrylic acid ester in the (meth) acrylic resin is preferably at least 30 mol%, more preferably at least 50 mol%.
　特定重合体における、カルボキシ基を有するモノマーの共重合比の好ましい範囲は、特定重合体１００質量％に対して、５質量％～５０質量％であり、より好ましくは５質量％～４０質量％、更に好ましくは１０質量％～２０質量％の範囲内である。
　特定重合体は、反応性基を有していてもよい。
　反応性基を特定重合体に導入する手段としては、水酸基、カルボキシ基、第一級アミノ基、第二級アミノ基、アセトアセチル基、スルホン酸などに、エポキシ化合物、ブロックイソシアネート、イソシアネート、ビニルスルホン化合物、アルデヒド化合物、メチロール化合物、カルボン酸無水物などを反応させる方法が挙げられる。
　これらの中でも、反応性基としては、ラジカル重合性基であることが好ましく、エチレン性不飽和基であることがより好ましく、（メタ）アクリロキシ基であることが特に好ましい。 The preferred range of the copolymerization ratio of the monomer having a carboxy group in the specific polymer is 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, with respect to 100% by mass of the specific polymer. More preferably, it is in the range of 10% by mass to 20% by mass.
The specific polymer may have a reactive group.
Means for introducing a reactive group into the specific polymer include a hydroxyl group, a carboxy group, a primary amino group, a secondary amino group, an acetoacetyl group, a sulfonic acid, an epoxy compound, a blocked isocyanate, an isocyanate, and a vinyl sulfone. A method of reacting a compound, an aldehyde compound, a methylol compound, a carboxylic anhydride, or the like can be used.
Among these, the reactive group is preferably a radical polymerizable group, more preferably an ethylenically unsaturated group, and particularly preferably a (meth) acryloxy group.
　また、バインダーポリマー（特に特定重合体）は、硬化後の透湿度及び強度の観点から、芳香環を有する構成単位を有していてもよい。
　芳香環を有する構成単位を形成するモノマーとしては、スチレン、ｔｅｒｔ－ブトキシスチレン、４－メチルスチレン、α－メチルスチレン、ベンジル（メタ）アクリレート等が挙げられる。
　また、芳香環を有する構成単位としては、スチレン由来の構成単位であることが好ましい。 Further, the binder polymer (particularly, the specific polymer) may have a structural unit having an aromatic ring from the viewpoint of moisture permeability and strength after curing.
Examples of the monomer forming the structural unit having an aromatic ring include styrene, tert-butoxystyrene, 4-methylstyrene, α-methylstyrene, benzyl (meth) acrylate, and the like.
The constituent unit having an aromatic ring is preferably a constituent unit derived from styrene.
　バインダーポリマーが芳香環を有する構成単位を含有する場合、芳香環を有する構成単位の含有量は、バインダーポリマーの全質量に対し、５質量％～９０質量％であることが好ましく、１０質量％～７０質量％であることがより好ましく、２０質量％～５０質量％であることが更に好ましい。 When the binder polymer contains a constituent unit having an aromatic ring, the content of the constituent unit having an aromatic ring is preferably from 5% by mass to 90% by mass, and more preferably from 10% by mass to 90% by mass, based on the total mass of the binder polymer. The content is more preferably 70% by mass, and even more preferably 20% by mass to 50% by mass.
　また、バインダーポリマー、特に特定重合体は、タック性、及び、硬化後の強度の観点から、脂肪族環式骨格を有する構成単位を有することが好ましい。
　脂肪族環式骨格を有する構成単位を形成するモノマーとして、具体的には、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）アクリレート等が挙げられる。
　上記脂肪族環式骨格を有する構成単位が有する脂肪族環としては、ジシクロペンタン環、シクロヘキサン環、イソボロン環、トリシクロデカン環等が好ましく挙げられる。中でも、トリシクロデカン環が特に好ましく挙げられる。 The binder polymer, particularly the specific polymer, preferably has a structural unit having an aliphatic cyclic skeleton from the viewpoint of tackiness and strength after curing.
Specific examples of the monomer forming the structural unit having an aliphatic cyclic skeleton include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
As the aliphatic ring contained in the structural unit having the aliphatic cyclic skeleton, a dicyclopentane ring, a cyclohexane ring, an isoboron ring, a tricyclodecane ring and the like are preferably exemplified. Among them, a tricyclodecane ring is particularly preferred.
　バインダーポリマーが脂肪族環式骨格を有する構成単位を含有する場合、脂肪族環式骨格を有する構成単位の含有量は、バインダーポリマーの全質量に対し、５質量％～９０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％であることが更に好ましい。 When the binder polymer contains a constituent unit having an alicyclic skeleton, the content of the constituent unit having an alicyclic skeleton may be 5% by mass to 90% by mass based on the total mass of the binder polymer. It is more preferably from 10% by mass to 80% by mass, and still more preferably from 20% by mass to 70% by mass.
　また、バインダーポリマー、特に特定重合体は、タック性、及び硬化後の強度の観点から、エチレン性不飽和基を有する構成単位を有することが好ましい。エチレン性不飽和基としては、（メタ）アクリル基が好ましく、（メタ）アクリロキシ基がより好ましい。
　バインダーポリマーがエチレン性不飽和基を有する構成単位を含有する場合、エチレン性不飽和基を有する構成単位の含有量は、バインダーポリマーの全質量に対し、５質量％～７０質量％であることが好ましく、１０質量％～５０質量％であることがより好ましく、２０質量％～４０質量％であることが更に好ましい。 In addition, the binder polymer, particularly the specific polymer, preferably has a structural unit having an ethylenically unsaturated group from the viewpoint of tackiness and strength after curing. As the ethylenically unsaturated group, a (meth) acryl group is preferable, and a (meth) acryloxy group is more preferable.
When the binder polymer contains a constituent unit having an ethylenically unsaturated group, the content of the constituent unit having an ethylenically unsaturated group may be 5% by mass to 70% by mass based on the total mass of the binder polymer. It is more preferably from 10% by mass to 50% by mass, even more preferably from 20% by mass to 40% by mass.
　バインダーポリマーとしては、例えば、以下に示す化合物Ａ（Ｍｅはメチル基を示す。）が好適に挙げられる。なお、以下に示す各構成単位の含有比率は目的に応じて適宜変更することができる。
　バインダーポリマーは、上市されている市販品を用いてもよく、例えば、藤倉化成株式会社のアクリベース（登録商標）ＦＦＳ－６０５８、ＦＦ１８７、大成ファインケミカル株式会社のアクリット（登録商標）８ＫＢ－００１等の８ＫＢシリーズが挙げられる。 Preferred examples of the binder polymer include the following compound A (Me represents a methyl group). The content ratio of each structural unit shown below can be appropriately changed according to the purpose.
As the binder polymer, commercially available products may be used. For example, Acrybase (registered trademark) FFS-6058 and FF187 of Fujikura Kasei Co., Ltd., and Acryt (registered trademark) 8KB-001 of Taisei Fine Chemical Co., Ltd. may be used. 8KB series.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　バインダーポリマーの酸価は、６０ｍｇＫＯＨ／ｇ～２５０ｍｇＫＯＨ／ｇであることが好ましく、７０ｍｇＫＯＨ／ｇ～１８０ｍｇＫＯＨ／ｇであることが更に好ましい。 酸 The acid value of the binder polymer is preferably from 60 mgKOH / g to 250 mgKOH / g, more preferably from 70 mgKOH / g to 180 mgKOH / g.
　本開示において、酸価は、ＪＩＳ　Ｋ００７０（１９９２年）に記載の方法に準拠して測定される値である。以下同様である。 に お い て In the present disclosure, the acid value is a value measured according to the method described in JIS K0070 (1992). The same applies hereinafter.
　バインダーポリマーが、酸価６０ｍｇＫＯＨ／ｇ以上のバインダーポリマーを含むことで、既述の利点に加え、後述する遮光層が酸基を有するアクリル樹脂を含有することにより、第１感光層と遮光層との間の密着性を高めることができる。 When the binder polymer contains a binder polymer having an acid value of 60 mgKOH / g or more, in addition to the above-mentioned advantages, the first light-shielding layer and the light-shielding layer Between them can be improved.
　また、バインダーポリマーは、上記のポリマー以外にも、任意の膜形成樹脂を目的に応じて適宜選択して用いることができる。 バ イ ン ダ ー As the binder polymer, any film-forming resin other than the above-mentioned polymers can be appropriately selected and used according to the purpose.
　バインダーポリマーの重量平均分子量は、特に制限はないが、３，０００を超えることが好ましく、３，０００を超え６０，０００以下であることがより好ましく、５，０００～５０，０００であることが更に好ましい。
　重量平均分子量の測定は、後述する遮光層に用いられるバインダーポリマーの重量平均分子量の測定と同様の方法及び条件にて、ゲル透過クロマトグラフ（ＧＰＣ）により行うことができる。 The weight average molecular weight of the binder polymer is not particularly limited, but is preferably more than 3,000, more preferably more than 3,000 and not more than 60,000, and more preferably 5,000 to 50,000. More preferred.
The measurement of the weight average molecular weight can be performed by gel permeation chromatography (GPC) by the same method and under the same conditions as the measurement of the weight average molecular weight of the binder polymer used in the light-shielding layer described later.
　バインダーポリマーは、１種単独で使用しても、２種以上を含有してもよい。
　バインダーポリマーの第１感光層中における含有量は、感光性及び硬化膜の強度の観点から、第１感光層の全質量に対して、１０質量％～９０質量％が好ましく、１５質量％以上８０質量％以下がより好ましく、２０質量％以上７０質量％以下が更に好ましい。 The binder polymer may be used alone, or may contain two or more kinds.
The content of the binder polymer in the first photosensitive layer is preferably from 10% by mass to 90% by mass, more preferably from 15% by mass to 80% by mass, based on the total mass of the first photosensitive layer, from the viewpoint of photosensitivity and the strength of the cured film. % By mass or less, more preferably 20% by mass or more and 70% by mass or less.
－重合性化合物－
　第１感光層は、重合性化合物の少なくとも一種を含有する。
　重合性化合物は、第１感光層の感光性（即ち、光硬化性）及び硬化膜の強度に寄与する成分である。本開示における重合性化合物は、１つ以上のエチレン性不飽和基を有する化合物（以下、「エチレン性不飽和化合物」ともいう。）である。中でも、重合性化合物は、光照射により活性種としてラジカルを放出するラジカル重合性化合物が好ましい。 -Polymerizable compound-
The first photosensitive layer contains at least one polymerizable compound.
The polymerizable compound is a component that contributes to the photosensitivity (that is, photocurability) of the first photosensitive layer and the strength of the cured film. The polymerizable compound in the present disclosure is a compound having one or more ethylenically unsaturated groups (hereinafter, also referred to as “ethylenically unsaturated compound”). Above all, the polymerizable compound is preferably a radical polymerizable compound that releases a radical as an active species by light irradiation.
　第１感光層は、エチレン性不飽和化合物として、２官能以上のエチレン性不飽和化合物を含むことが好ましい。
　ここで、２官能以上のエチレン性不飽和化合物とは、一分子中にエチレン性不飽和基を２つ以上有する化合物を意味する。
　エチレン性不飽和基としては、（メタ）アクリロイル基がより好ましい。
　エチレン性不飽和化合物としては、（メタ）アクリレート化合物が好ましい。 The first photosensitive layer preferably contains a bifunctional or higher functional ethylenically unsaturated compound as the ethylenically unsaturated compound.
Here, the bifunctional or higher functional ethylenically unsaturated compound means a compound having two or more ethylenically unsaturated groups in one molecule.
As the ethylenically unsaturated group, a (meth) acryloyl group is more preferred.
As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.
　第１感光層は、硬化後の硬化性の観点から、２官能のエチレン性不飽和化合物（好ましくは、２官能の（メタ）アクリレート化合物）と、３官能以上のエチレン性不飽和化合物（好ましくは、３官能以上の（メタ）アクリレート化合物）と、を含有することが特に好ましい。 From the viewpoint of curability after curing, the first photosensitive layer includes a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth) acrylate compound) and a trifunctional or higher functional ethylenically unsaturated compound (preferably And a (meth) acrylate compound having three or more functional groups).
　２官能のエチレン性不飽和化合物としては、特に制限はなく、公知の化合物の中から適宜選択できる。
　２官能のエチレン性不飽和化合物としては、トリシクロデカンジメタノールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート等が挙げられる。
　２官能のエチレン性不飽和化合物としては、より具体的には、トリシクロデカンジメタノールジアクリレート（Ａ－ＤＣＰ、新中村化学工業（株）製）、トリシクロデカンジメタノールジメタクリレート（ＤＣＰ、新中村化学工業（株）製）、１，９－ノナンジオールジアクリレート（Ａ－ＮＯＤ－Ｎ、新中村化学工業（株）製）、１，６－ヘキサンジオールジアクリレート（Ａ－ＨＤ－Ｎ、新中村化学工業（株）製）等が挙げられる。 The bifunctional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds.
Examples of the bifunctional ethylenically unsaturated compound include tricyclodecane dimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,6-hexane. And diol di (meth) acrylate.
As the bifunctional ethylenically unsaturated compound, more specifically, tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, new 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, new Nakamura Chemical Industry Co., Ltd.).
　３官能以上のエチレン性不飽和化合物としては、特に制限はなく、公知の化合物の中から適宜選択できる。
　３官能以上のエチレン性不飽和化合物としては、例えば、ジペンタエリスリトール（トリ／テトラ／ペンタ／ヘキサ）（メタ）アクリレート、ペンタエリスリトール（トリ／テトラ）（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、イソシアヌル酸（メタ）アクリレート、グリセリントリ（メタ）アクリレート骨格の（メタ）アクリレート化合物、等が挙げられる。 The trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.
Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth) Examples include acrylate, ditrimethylolpropanetetra (meth) acrylate, isocyanuric acid (meth) acrylate, and a (meth) acrylate compound having a glycerin tri (meth) acrylate skeleton.
　ここで、「（トリ／テトラ／ペンタ／ヘキサ）（メタ）アクリレート」は、トリ（メタ）アクリレート、テトラ（メタ）アクリレート、ペンタ（メタ）アクリレート、及びヘキサ（メタ）アクリレートを包含する概念であり、「（トリ／テトラ）（メタ）アクリレート」は、トリ（メタ）アクリレート及びテトラ（メタ）アクリレートを包含する概念である。 Here, “(tri / tetra / penta / hexa) (meth) acrylate” is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. , “(Tri / tetra) (meth) acrylate” is a concept including tri (meth) acrylate and tetra (meth) acrylate.
　エチレン性不飽和化合物としては、（メタ）アクリレート化合物のカプロラクトン変性化合物（日本化薬（株）製ＫＡＹＡＲＡＤ（登録商標）ＤＰＣＡ－２０、新中村化学工業（株）製Ａ－９３００－１ＣＬ等）、（メタ）アクリレート化合物のアルキレンオキサイド変性化合物（日本化薬（株）製ＫＡＹＡＲＡＤ　ＲＰ－１０４０、新中村化学工業（株）製ＡＴＭ－３５Ｅ、Ａ－９３００、ダイセル・オルネクス社製　ＥＢＥＣＲＹＬ（登録商標）　１３５等）、エトキシル化グリセリントリアクリレート（新中村化学工業（株）製Ａ－ＧＬＹ－９Ｅ等）等も挙げられる。 Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth) acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), Alkylene oxide-modified compound of (meth) acrylate compound (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex) Ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.
　エチレン性不飽和化合物としては、ウレタン（メタ）アクリレート化合物（好ましくは３官能以上のウレタン（メタ）アクリレート化合物）も挙げられる。
　３官能以上のウレタン（メタ）アクリレート化合物としては、例えば、８ＵＸ－０１５Ａ（大成ファインケミカル（株）製）、ＵＡ－３２Ｐ（新中村化学工業（株）製）、ＵＡ－１１００Ｈ（新中村化学工業（株）製）等が挙げられる。 Examples of the ethylenically unsaturated compound also include a urethane (meth) acrylate compound (preferably a trifunctional or higher functional urethane (meth) acrylate compound).
Examples of trifunctional or higher functional urethane (meth) acrylate compounds include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.) Co., Ltd.).
　また、エチレン性不飽和化合物は、現像性向上の観点から、酸基を有するエチレン性不飽和化合物を含むことが好ましい。
　酸基としては、例えば、リン酸基、スルホン酸基、及び、カルボキシ基が挙げられ、カルボキシ基が好ましい。
　酸基を有するエチレン性不飽和化合物としては、例えば、酸基を有する３～４官能のエチレン性不飽和化合物（ペンタエリスリトールトリ及びテトラアクリレート（ＰＥＴＡ）骨格にカルボキシ基を導入したもの（酸価＝８０～１２０ｍｇＫＯＨ／ｇ））、酸基を有する５～６官能のエチレン性不飽和化合物（ジペンタエリスリトールペンタ及びヘキサアクリレート（ＤＰＨＡ）骨格にカルボキシ基を導入したもの（酸価＝２５～７０ｍｇＫＯＨ／ｇ））、等が挙げられる。
　これら酸基を有する３官能以上のエチレン性不飽和化合物は、必要に応じ、酸基を有する２官能のエチレン性不飽和化合物と併用してもよい。 In addition, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group from the viewpoint of improving developability.
Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxy group, and a carboxy group is preferable.
Examples of the ethylenically unsaturated compound having an acid group include a tri- or tetrafunctional ethylenically unsaturated compound having an acid group (pentaerythritol tri and tetraacrylate (PETA) having a carboxy group introduced into the skeleton (acid value = 80-120 mg KOH / g), 5-6 functional ethylenically unsaturated compounds having an acid group (dipentaerythritol penta and hexaacrylate (DPHA) having a carboxy group introduced into the skeleton thereof (acid value = 25-70 mg KOH / g) )) And the like.
These trifunctional or more ethylenically unsaturated compounds having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, if necessary.
　酸基を有するエチレン性不飽和化合物としては、カルボキシ基を含有する２官能以上のエチレン性不飽和化合物及びそのカルボン酸無水物よりなる群から選ばれる少なくとも１種が好ましい。これにより現像性、及び、硬化膜の強度が高まる。
　カルボキシ基を含有する２官能以上のエチレン性不飽和化合物は、特に制限されず、公知の化合物の中から適宜選択できる。
　カルボキシ基を含有する２官能以上のエチレン性不飽和化合物としては、例えば、アロニックス（登録商標）ＴＯ－２３４９ＭＥ（東亞合成（株）製）、アロニックスＭ－５２０（東亞合成（株）製）、又は、アロニックスＭ－５１０（東亞合成（株）製）を好ましく用いることができる。 As the ethylenically unsaturated compound having an acid group, at least one selected from the group consisting of bifunctional or more functional ethylenically unsaturated compounds having a carboxy group and carboxylic anhydrides thereof is preferable. This increases the developability and the strength of the cured film.
The bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group is not particularly limited, and can be appropriately selected from known compounds.
Examples of the bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group include ARONIX (registered trademark) TO-2349ME (manufactured by Toagosei Co., Ltd.), ARONIX M-520 (manufactured by Toagosei Co., Ltd.), or And Aronix M-510 (manufactured by Toagosei Co., Ltd.) can be preferably used.
　酸基を有するエチレン性不飽和化合物は、特開２００４－２３９９４２号公報の段落００２５～００３０に記載の酸基を有する重合性化合物であることも好ましい。この公報の内容は本開示に組み込まれる。 It is also preferable that the ethylenically unsaturated compound having an acid group is a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942. The contents of this publication are incorporated into the present disclosure.
　本開示に用いられるエチレン性不飽和化合物の重量平均分子量（Ｍｗ）としては、２００～３，０００が好ましく、２５０～２，６００がより好ましく、２８０～２，２００が更に好ましく、３００～２，２００が特に好ましい。
　また、第１感光層に用いられるエチレン性不飽和化合物のうち、分子量３００以下のエチレン性不飽和化合物の含有量の割合は、第１感光層に含有されるすべてのエチレン性不飽和化合物に対して、３０質量％以下が好ましく、２５質量％以下がより好ましく、２０質量％以下が更に好ましい。 The weight average molecular weight (Mw) of the ethylenically unsaturated compound used in the present disclosure is preferably from 200 to 3,000, more preferably from 250 to 2,600, still more preferably from 280 to 2,200, and more preferably from 300 to 2,200. 200 is particularly preferred.
Further, among the ethylenically unsaturated compounds used in the first photosensitive layer, the proportion of the content of the ethylenically unsaturated compound having a molecular weight of 300 or less is relative to all the ethylenically unsaturated compounds contained in the first photosensitive layer. Thus, the content is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.
　エチレン性不飽和化合物は、１種単独で使用しても、２種以上を併用してもよい。
　第１感光層におけるエチレン性不飽和化合物の含有量は、第１感光層の全質量に対し、１質量％～７０質量％が好ましく、１０質量％～７０質量％がより好ましく、２０質量％～６０質量％が更に好ましく、２０質量％～５０質量％が特に好ましい。 Ethylenically unsaturated compounds may be used alone or in combination of two or more.
The content of the ethylenically unsaturated compound in the first photosensitive layer is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 70% by mass, and more preferably 20% by mass to the total mass of the first photosensitive layer. 60 mass% is more preferable, and 20 mass% to 50 mass% is particularly preferable.
　また、第１感光層が２官能のエチレン性不飽和化合物と３官能以上のエチレン性不飽和化合物とを含有する場合、２官能のエチレン性不飽和化合物の含有量は、第１感光層に含まれる全てのエチレン性不飽和化合物に対し、１０質量％～９０質量％が好ましく、２０質量％～８５質量％がより好ましく、３０質量％～８０質量％が更に好ましい。
　また、この場合、３官能以上のエチレン性不飽和化合物の含有量は、第１感光層に含まれる全てのエチレン性不飽和化合物に対し、１０質量％～９０質量％が好ましく、１５質量％～８０質量％がより好ましく、２０質量％～７０質量％が更に好ましい。
　また、この場合、２官能以上のエチレン性不飽和化合物の含有量は、２官能のエチレン性不飽和化合物と３官能以上のエチレン性不飽和化合物との総含有量に対し、４０質量％以上１００質量％未満であることが好ましく、４０質量％～９０質量％であることがより好ましく、５０質量％～８０質量％であることが更に好ましく、５０質量％～７０質量％であることが特に好ましい。 When the first photosensitive layer contains a bifunctional ethylenically unsaturated compound and a trifunctional or more ethylenically unsaturated compound, the content of the bifunctional ethylenically unsaturated compound is included in the first photosensitive layer. 10% by mass to 90% by mass, more preferably 20% by mass to 85% by mass, even more preferably 30% by mass to 80% by mass, based on all the ethylenically unsaturated compounds obtained.
In this case, the content of the trifunctional or higher-functional ethylenically unsaturated compound is preferably from 10% by mass to 90% by mass, more preferably from 15% by mass to 90% by mass, based on all the ethylenically unsaturated compounds contained in the first photosensitive layer. 80 mass% is more preferable, and 20 mass% to 70 mass% is even more preferable.
In this case, the content of the bifunctional or more ethylenically unsaturated compound is 40% by mass or more with respect to the total content of the bifunctional ethylenically unsaturated compound and the trifunctional or more ethylenically unsaturated compound. It is preferably less than 40% by mass, more preferably 40% by mass to 90% by mass, still more preferably 50% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass. .
　また、第１感光層が２官能以上のエチレン性不飽和化合物を含有する場合、第１感光層は、更に単官能エチレン性不飽和化合物を含有してもよい。
　更に、第１感光層が２官能以上のエチレン性不飽和化合物を含有する場合、第１感光層に含有されるエチレン性不飽和化合物において、２官能以上のエチレン性不飽和化合物が主成分であることが好ましい。
　具体的には、第１感光層が２官能以上のエチレン性不飽和化合物を含有する場合において、２官能以上のエチレン性不飽和化合物の含有量は、第１感光層に含有されるエチレン性不飽和化合物の総含有量に対し、４０質量％～１００質量％が好ましく、５０質量％～１００質量％がより好ましく、６０質量％～１００質量％が特に好ましい。 When the first photosensitive layer contains a bifunctional or more functional ethylenically unsaturated compound, the first photosensitive layer may further contain a monofunctional ethylenically unsaturated compound.
Further, when the first photosensitive layer contains a bifunctional or higher functional ethylenically unsaturated compound, the bifunctional or higher functional ethylenically unsaturated compound is a main component in the ethylenically unsaturated compound contained in the first photosensitive layer. Is preferred.
Specifically, when the first photosensitive layer contains a bifunctional or higher functional ethylenically unsaturated compound, the content of the bifunctional or higher functional ethylenically unsaturated compound is controlled by the ethylenically unsaturated compound contained in the first photosensitive layer. It is preferably from 40% by mass to 100% by mass, more preferably from 50% by mass to 100% by mass, particularly preferably from 60% by mass to 100% by mass, based on the total content of the saturated compound.
　また、第１感光層が、酸基を有するエチレン性不飽和化合物（好ましくは、カルボキシ基を含有する２官能以上のエチレン性不飽和化合物又はそのカルボン酸無水物）を含有する場合、酸基を有するエチレン性不飽和化合物の含有量は、第１感光層の全質量に対し、０．５質量％～５０質量％が好ましく、０．５質量％～２０質量％がより好ましく、０．５質量％～１０質量％が更に好ましい。 When the first photosensitive layer contains an ethylenically unsaturated compound having an acid group (preferably, a bifunctional or more functional ethylenically unsaturated compound having a carboxy group or a carboxylic anhydride thereof), The content of the ethylenically unsaturated compound is preferably 0.5% by mass to 50% by mass, more preferably 0.5% by mass to 20% by mass, and preferably 0.5% by mass to the total mass of the first photosensitive layer. % To 10% by mass is more preferred.
－光重合開始剤－
　第１感光層は、光重合開始剤の少なくとも一種を含有する。
　光重合開始剤としては特に制限はなく、公知の光重合開始剤を用いることができる。
　光重合開始剤としては、オキシムエステル構造を有する光重合開始剤（以下、「オキシム系光重合開始剤」ともいう。）、α－アミノアルキルフェノン構造を有する光重合開始剤（以下、「α－アミノアルキルフェノン系光重合開始剤」ともいう。）、α－ヒドロキシアルキルフェノン構造を有する光重合開始剤（以下、「α－ヒドロキシアルキルフェノン系重合開始剤」ともいう。）、アシルフォスフィンオキサイド構造を有する光重合開始剤（以下、「アシルフォスフィンオキサイド系光重合開始剤」ともいう。）、Ｎ－フェニルグリシン構造を有する光重合開始剤（以下、「Ｎ－フェニルグリシン系光重合開始剤」ともいう。）等が挙げられる。 -Photopolymerization initiator-
The first photosensitive layer contains at least one photopolymerization initiator.
The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as an “oxime-based photopolymerization initiator”) and a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter, “α- Aminoalkylphenone-based photopolymerization initiator "), photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as" α-hydroxyalkylphenone-based polymerization initiator "), acylphosphine oxide structure (Hereinafter also referred to as “acylphosphine oxide-based photopolymerization initiator”), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter “N-phenylglycine-based photopolymerization initiator”) ).
　光重合開始剤は、オキシム系光重合開始剤、α－アミノアルキルフェノン系光重合開始剤、α－ヒドロキシアルキルフェノン系重合開始剤及びＮ－フェニルグリシン系光重合開始剤よりなる群から選ばれる少なくとも１種を含むことが好ましく、オキシム系光重合開始剤、α－アミノアルキルフェノン系光重合開始剤及びＮ－フェニルグリシン系光重合開始剤よりなる群から選ばれる少なくとも１種を含むことがより好ましい。 The photopolymerization initiator is at least selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, an α-hydroxyalkylphenone-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator. It is preferable to include at least one kind, more preferably at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator. .
　また、光重合開始剤としては、例えば、特開２０１１－９５７１６号公報の段落００３１～００４２、特開２０１５－０１４７８３号公報の段落００６４～００８１に記載された重合開始剤を用いてもよい。 As the photopolymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-014783 may be used.
　光重合開始剤の市販品としては、１－［４－（フェニルチオ）］－１，２－オクタンジオン－２－（Ｏ－ベンゾイルオキシム）（商品名：ＩＲＧＡＣＵＲＥ（登録商標）　ＯＸＥ－０１、ＢＡＳＦ社製）、１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン－１－（Ｏ－アセチルオキシム）（商品名：ＩＲＧＡＣＵＲＥ　ＯＸＥ－０２、ＢＡＳＦ社製）、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン（商品名：ＩＲＧＡＣＵＲＥ　３７９ＥＧ、ＢＡＳＦ社製）、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン（商品名：ＩＲＧＡＣＵＲＥ　９０７、ＢＡＳＦ社製）、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）ベンジル］フェニル｝－２－メチルプロパン－１－オン（商品名：ＩＲＧＡＣＵＲＥ　１２７、ＢＡＳＦ社製）、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１（商品名：ＩＲＧＡＣＵＲＥ　３６９、ＢＡＳＦ社製）、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン（商品名：ＩＲＧＡＣＵＲＥ　１１７３、ＢＡＳＦ社製）、１－ヒドロキシシクロヘキシルフェニルケトン（商品名：ＩＲＧＡＣＵＲＥ　１８４、ＢＡＳＦ社製）、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（商品名：ＩＲＧＡＣＵＲＥ　６５１、ＢＡＳＦ社製）、オキシムエステル系光重合開始剤（商品名：Ｌｕｎａｒ　６、ＤＫＳＨジャパン（株）製）などが挙げられる。 Commercially available photopolymerization initiators include 1- [4- (phenylthio)]-1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE® OXE-01, BASF) 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) (trade name: IRGACURE @ OXE-02, manufactured by BASF) 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE @ 379EG, BASF), 2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE @ 907, manufactured by BASF), 2- Droxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) benzyl] phenyl} -2-methylpropan-1-one (trade name: IRGACURE 127, manufactured by BASF), 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE # 369, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name) : 1-hydroxycyclohexylphenyl ketone (trade name: IRGACURE 184, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: IRGACURE 651, BASF), an oxime ester-based photopolymerization initiator (trade name: Lun r 6, DKSH manufactured by Japan Co., Ltd.), and the like.
　光重合開始剤は、１種単独で使用しても、２種以上を併用してもよい。
　第１感光層における光重合開始剤の含有量は、特に制限はないが、第１感光層の全質量に対し、０．１質量％以上が好ましく、０．５質量％以上がより好ましい。また、光重合開始剤の含有量は、第１感光層の全質量に対し、１０質量％以下が好ましく、５質量％以下がより好ましい。 The photopolymerization initiator may be used alone or in combination of two or more.
The content of the photopolymerization initiator in the first photosensitive layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more based on the total mass of the first photosensitive layer. Further, the content of the photopolymerization initiator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the first photosensitive layer.
－界面活性剤－
　第１感光層は、界面活性剤の少なくとも一種を含有することができる。
　界面活性剤としては、例えば、特許第４５０２７８４号公報の段落００１７及び特開２００９－２３７３６２号公報の段落００６０～００７１に記載の界面活性剤、公知のフッ素系界面活性剤等を用いることができる。
　界面活性剤としては、フッ素系界面活性剤が好ましい。
　フッ素系界面活性剤の市販品としては、メガファック（登録商標）Ｆ－５５１Ａ（ＤＩＣ（株）製）が挙げられる。 -Surfactant-
The first photosensitive layer can contain at least one surfactant.
As the surfactant, for example, the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362, known fluorine-based surfactants, and the like can be used.
As the surfactant, a fluorine-based surfactant is preferable.
Examples of commercially available fluorine-based surfactants include Megafac (registered trademark) F-551A (manufactured by DIC Corporation).
　第１感光層が界面活性剤を含有する場合、界面活性剤の第１感光層中における含有量としては、第１感光層の全質量に対して、０．０１質量％～３質量％が好ましく、０．０５質量％～１質量％がより好ましく、０．１質量％～０．８質量％が更に好ましい。 When the first photosensitive layer contains a surfactant, the content of the surfactant in the first photosensitive layer is preferably 0.01% by mass to 3% by mass based on the total mass of the first photosensitive layer. , 0.05% by mass to 1% by mass, more preferably 0.1% by mass to 0.8% by mass.
－他の成分－
　第１感光層は、上記した成分に加え、必要に応じて、添加剤等の他の成分を含んでいてもよい。 -Other components-
The first photosensitive layer may contain other components such as additives, if necessary, in addition to the components described above.
（ブロックイソシアネート化合物）
　感光性層は、硬化後の硬度の観点から、ブロックイソシアネート化合物を更に含有することができる。
　なお、ブロックイソシアネート化合物とは、「イソシアネートのイソシアネート基をブロック剤で保護（マスク）した構造を有する化合物」のことをいう。 (Blocked isocyanate compound)
The photosensitive layer can further contain a blocked isocyanate compound from the viewpoint of hardness after curing.
In addition, the blocked isocyanate compound means a "compound having a structure in which an isocyanate group of isocyanate is protected (masked) with a blocking agent".
　ブロックイソシアネート化合物の解離温度は、１００℃～１６０℃であることが好ましく、１３０℃～１５０℃であることがより好ましい。
　本明細書中におけるブロックイソシアネートの解離温度とは、「示差走査熱量計（セイコーインスツルメンツ（株）製、ＤＳＣ６２００）によりＤＳＣ（Ｄｉｆｆｅｒｅｎｔｉａｌ　ｓｃａｎｎｉｎｇ　ｃａｌｏｒｉｍｅｔｒｙ）分析にて測定した場合に、ブロックイソシアネートの脱保護反応に伴う吸熱ピークの温度」のことをいう。 The dissociation temperature of the blocked isocyanate compound is preferably from 100 ° C to 160 ° C, more preferably from 130 ° C to 150 ° C.
The dissociation temperature of a blocked isocyanate in the present specification is defined as "a deprotection reaction of a blocked isocyanate when measured by a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.) by DSC (Differential scanning calorimetry) analysis". Accompanying endothermic peak temperature ".
　解離温度が１００℃～１６０℃であるブロック剤としては、ピラゾール化合物（３，５－ジメチルピラゾール、３－メチルピラゾール、４－ブロモ－３，５－ジメチルピラゾール、４－ニトロ－３，５－ジメチルピラゾールなど）、活性メチレン化合物（マロン酸ジエステル（マロン酸ジメチル、マロン酸ジエチル、マロン酸ジｎ－ブチル、マロン酸ジ２－エチルヘキシル）など）、トリアゾール化合物（１，２，４－トリアゾールなど）、オキシム化合物（ホルムアルドキシム、アセトアルドキシム、アセトキシム、メチルエチルケトキシム、シクロヘキサノンオキシムなどの分子内に－Ｃ（＝Ｎ－ＯＨ）－で表される構造を有する化合物）などが挙げられる。中でも、保存安定性の観点から、オキシム化合物、又は、ピラゾール化合物が好ましく、オキシム化合物が特に好ましい。 Examples of the blocking agent having a dissociation temperature of 100 ° C. to 160 ° C. include pyrazole compounds (3,5-dimethylpyrazole, 3-methylpyrazole, 4-bromo-3,5-dimethylpyrazole, 4-nitro-3,5-dimethyl Active methylene compounds (eg, malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate)), triazole compounds (eg, 1,2,4-triazole), Oxime compounds (compounds having a structure represented by —C (＝ N—OH) — in the molecule, such as formaldoxime, acetoaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime). Among them, from the viewpoint of storage stability, an oxime compound or a pyrazole compound is preferable, and an oxime compound is particularly preferable.
　また、ブロックイソシアネート化合物がイソシアヌレート構造を有することが膜の脆性改良、被転写体との密着力向上等の観点から好ましい。イソシアヌレート構造を有するブロックイソシアネート化合物は、例えばヘキサメチレンジイソシアネートをイソシアヌレート化して保護することにより調製することができる。
　イソシアヌレート構造を有するブロックイソシアネート化合物の中でも、オキシム化合物をブロック剤として用いたオキシム構造を有する化合物が、オキシム構造を有さない化合物よりも解離温度を好ましい範囲にしやすく、現像残渣を少なくしやすい観点から好ましい。 In addition, it is preferable that the blocked isocyanate compound has an isocyanurate structure from the viewpoint of improving the brittleness of the film, improving the adhesion to the transfer target, and the like. The blocked isocyanate compound having an isocyanurate structure can be prepared, for example, by protecting hexamethylene diisocyanate by isocyanuration.
Among the blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are more likely to have a dissociation temperature in a preferable range than compounds having no oxime structure, and are likely to reduce development residues. Is preferred.
　本開示に用いられるブロックイソシアネート化合物は、硬化後の硬度の観点から、ラジカル重合性基を有することが好ましい。
　ラジカル重合性基としては、特に制限はなく、公知の重合性基を用いることができ、例えば、（メタ）アクリロキシ基、（メタ）アクリルアミド基、スチリル基等のエチレン性不飽和基、グリシジル基等のエポキシ基を有する基などが挙げられる。中でも、重合性基としては、得られる硬化膜における表面の面状、現像速度及び反応性の観点から、エチレン性不飽和基であることが好ましく、（メタ）アクリロキシ基であることがより好ましい。 The blocked isocyanate compound used in the present disclosure preferably has a radical polymerizable group from the viewpoint of hardness after curing.
The radical polymerizable group is not particularly limited, and a known polymerizable group can be used. Examples thereof include an ethylenically unsaturated group such as a (meth) acryloxy group, a (meth) acrylamide group, a styryl group, and a glycidyl group. And a group having an epoxy group. Above all, the polymerizable group is preferably an ethylenically unsaturated group, and more preferably a (meth) acryloxy group, from the viewpoint of the surface condition, development speed and reactivity of the obtained cured film.
　本開示に用いられるブロックイソシアネート化合物としては、市販のブロックイソシアネート化合物を挙げることもできる。例えば、カレンズＡＯＩ－ＢＭ、カレンズＭＯＩ－ＢＭ、カレンズＭＯＩ－ＢＰ（いずれも昭和電工（株）製）、ブロック型のデュラネートシリーズ（旭化成ケミカルズ（株）製）などを挙げることができる。 ブ ロ ッ ク As the blocked isocyanate compound used in the present disclosure, a commercially available blocked isocyanate compound can also be mentioned. For example, Karenz AOI-BM, Karenz MOI-BM, Karenz MOI-BP (all manufactured by Showa Denko KK), block type duranate series (manufactured by Asahi Kasei Chemicals Corporation) and the like can be mentioned.
　本開示に用いられるブロックイソシアネート化合物は、分子量が２００～３，０００であることが好ましく、２５０～２，６００であることがより好ましく、２８０～２，２００であることが特に好ましい。 ブ ロ ッ ク The blocked isocyanate compound used in the present disclosure preferably has a molecular weight of 200 to 3,000, more preferably 250 to 2,600, and particularly preferably 280 to 2,200.
　本開示においては、ブロックイソシアネート化合物を１種単独で使用しても、２種以上を併用してもよい。
　ブロックイソシアネート化合物の含有量は、第１感光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、５質量％～３０質量％であることがより好ましい。 In the present disclosure, one type of blocked isocyanate compound may be used alone, or two or more types may be used in combination.
The content of the blocked isocyanate compound is preferably from 1% by mass to 50% by mass, more preferably from 5% by mass to 30% by mass, based on the total mass of the first photosensitive layer.
（重合禁止剤）
　第１感光層は、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（重合禁止剤ともいう）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 first photosensitive layer may contain at least one polymerization inhibitor.
As the polymerization inhibitor, for example, a thermal polymerization inhibitor (also referred to as a polymerization inhibitor) described in paragraph 0018 of Japanese Patent No. 4502784 can be used.
Among them, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.
　第１感光層が重合禁止剤を含有する場合、重合禁止剤の含有量は、第１感光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 first photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, and more preferably 0.01% by mass to 3% by mass based on the total mass of the first photosensitive layer. 1% by mass is more preferable, and 0.01% by mass to 0.8% by mass is further preferable.
（水素供与性化合物）
　第１感光層は、水素供与性化合物を更に含有することができる。
　水素供与性化合物は、光重合開始剤の活性光線に対する感度を一層向上させる、又は酸素による重合性化合物の重合阻害を抑制する等の作用を有する。
　水素供与性化合物の例としては、アミン類、例えば、Ｍ．Ｒ．Ｓａｎｄｅｒら著「Ｊｏｕｒｎａｌ　ｏｆ　Ｐｏｌｙｍｅｒ　Ｓｏｃｉｅｔｙ」第１０巻３１７３頁（１９７２）、特公昭４４－２０１８９号公報、特開昭５１－８２１０２号公報、特開昭５２－１３４６９２号公報、特開昭５９－１３８２０５号公報、特開昭６０－８４３０５号公報、特開昭６２－１８５３７号公報、特開昭６４－３３１０４号公報、Ｒｅｓｅａｒｃｈ　Ｄｉｓｃｌｏｓｕｒｅ　３３８２５号記載の化合物等が挙げられ、具体的には、トリエタノールアミン、ｐ－ジメチルアミノ安息香酸エチルエステル、ｐ－ホルミルジメチルアニリン、ｐ－メチルチオジメチルアニリン等が挙げられる。 (Hydrogen donating compound)
The first photosensitive layer can further contain a hydrogen donating compound.
The hydrogen-donating compound has effects such as further improving the sensitivity of the photopolymerization initiator to actinic rays or suppressing polymerization inhibition of the polymerizable compound by oxygen.
Examples of the hydrogen donating compound include amines such as M.P. R. Sander et al., "Journal of Polymer Society", vol. 10, p. 3173 (1972), JP-B-44-20189, JP-A-51-82102, JP-A-52-134692, and JP-A-59-138205. And JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, and Research Disclosure 33825. Specific examples include triethanolamine. , P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.
　また、水素供与性化合物の更に別の例としては、アミノ酸化合物（例、Ｎ－フェニルグリシン等）、特公昭４８－４２９６５号公報記載の有機金属化合物（例、トリブチル錫アセテート等）、特公昭５５－３４４１４号公報記載の水素供与体、特開平６－３０８７２７号公報記載のイオウ化合物（例、トリチアン等）等が挙げられる。 Further examples of the hydrogen donating compound include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate, etc.), and JP-B-55 And hydrogen compounds described in JP-A-6-308727 (eg, trithiane).
　これら水素供与性化合物の含有量は、重合成長速度と連鎖移動のバランスによる硬化速度の向上の観点から、第１感光層の全質量に対し、０．１質量％以上３０質量％以下の範囲が好ましく、１質量％以上２５質量％以下の範囲がより好ましく、０．５質量％以上２０質量％以下の範囲が更に好ましい。 The content of these hydrogen-donating compounds is preferably in the range of 0.1% by mass or more and 30% by mass or less based on the total mass of the first photosensitive layer from the viewpoint of improving the curing speed by the balance between the polymerization growth rate and the chain transfer. The range is preferably from 1% by mass to 25% by mass, more preferably from 0.5% by mass to 20% by mass.
（その他の成分）
　第１感光層は、上述した成分以外のその他の成分を含有していてもよい。
　その他の成分としては、例えば、特許第４５０２７８４号公報の段落００１８に記載の熱重合防止剤、特開２０００－３１０７０６号公報の段落００５８～００７１に記載のその他の添加剤、等が挙げられる。 (Other components)
The first photosensitive layer may contain other components other than the components described above.
Examples of the other components include a thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784, and other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.
　また、第１感光層は、その他の成分として、屈折率や光透過性を調節することを目的として、粒子（例えば金属酸化物粒子）を少なくとも１種含んでもよい。
　金属酸化物粒子を構成する金属には、Ｂ、Ｓｉ、Ｇｅ、Ａｓ、Ｓｂ、Ｔｅ等の半金属も含まれる。硬化膜の透明性の観点から、粒子（例えば金属酸化物粒子）の平均一次粒子径は、１ｎｍ～２００ｎｍが好ましく、３ｎｍ～８０ｎｍがより好ましい。平均一次粒子径は、電子顕微鏡を用いて任意の粒子２００個の粒子径を測定し、測定結果を算術平均することにより算出される。粒子の形状が球形でない場合には、最も長い辺を粒子径とする。
　粒子の含有量は、第１感光層の全質量に対して、０質量％～３５質量％が好ましく、０質量％～１０質量％がより好ましく、０質量％～５質量％が更に好ましく、０質量％～１質量％が更に好ましく、０質量％（即ち、第１感光層に粒子が含まれないこと）が特に好ましい。 Further, the first photosensitive layer may include at least one kind of particles (for example, metal oxide particles) as another component for the purpose of adjusting the refractive index and the light transmittance.
Metals constituting the metal oxide particles include semimetals such as B, Si, Ge, As, Sb, and Te. From the viewpoint of the transparency of the cured film, the average primary particle diameter of the particles (eg, metal oxide particles) is preferably from 1 nm to 200 nm, more preferably from 3 nm to 80 nm. The average primary particle diameter is calculated by measuring the particle diameter of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. If the shape of the particles is not spherical, the longest side is the particle diameter.
The content of the particles is preferably 0% by mass to 35% by mass, more preferably 0% by mass to 10% by mass, still more preferably 0% by mass to 5% by mass, based on the total mass of the first photosensitive layer. The content is more preferably from 1% by mass to 1% by mass, and particularly preferably 0% by mass (that is, no particles are contained in the first photosensitive layer).
　また、第１感光層は、その他の成分として、微量の着色剤（顔料、染料、等）を含有してもよいが、透明性の観点から、着色剤を実質的に含有しないことが好ましい。
　具体的には、第１感光層における着色剤の含有量は、第１感光層の全質量に対し、１質量％未満が好ましく、０．１質量％未満がより好ましい。 In addition, the first photosensitive layer may contain a trace amount of a coloring agent (a pigment, a dye, or the like) as another component, but it is preferable that the first photosensitive layer does not substantially contain a coloring agent from the viewpoint of transparency.
Specifically, the content of the colorant in the first photosensitive layer is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the first photosensitive layer.
（不純物）
　第１感光層は、不純物の含有量が少ないことが好ましい。
　不純物の具体例としては、ナトリウム、カリウム、マグネシウム、カルシウム、鉄、マンガン、銅、アルミニウム、チタン、クロム、コバルト、ニッケル、亜鉛、スズ、及びこれらのイオン、並びに、遊離ハロゲン、ハロゲン化物イオン（塩化物イオン、臭化物イオン、ヨウ化物イオン等）などが挙げられる。
　不純物の第１感光層中における含有量は、質量基準で、１０００ｐｐｍ以下が好ましく、２００ｐｐｍ以下がより好ましく、４０ｐｐｍ以下がさらに好ましい。下限は特に定めるものではないが、現実的に減らせる限界及び測定限界の観点から、質量基準で、１０ｐｐｂ以上とすることができ、１００ｐｐｂ以上とすることができる。
　 不純物を上記範囲に減らす方法としては、樹脂及び添加剤の原料に不純物を含まないものを選択すること、及び層の形成時に不純物の混入を防ぐこと等が挙げられる。このような方法により、不純物量を上記範囲内とすることができる。
　不純物は、例えば、ＩＣＰ（Inductively Coupled Plasma）発光分光分析法、原子吸光分光法等の公知の方法で定量することができる。 (impurities)
The first photosensitive layer preferably has a low impurity content.
Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and their ions, as well as free halogen and halide ions (chloride Ion, bromide ion, iodide ion, etc.).
The content of the impurities in the first photosensitive layer is preferably 1000 ppm or less, more preferably 200 ppm or less, and still more preferably 40 ppm or less on a mass basis. Although the lower limit is not particularly defined, it can be set to 10 ppb or more and 100 ppb or more on a mass basis from the viewpoint of a limit that can be practically reduced and a measurement limit.
As a method of reducing impurities to the above range, there can be mentioned, for example, selecting a raw material of a resin and an additive that does not contain impurities, preventing mixing of impurities at the time of forming a layer, and the like. By such a method, the amount of impurities can be kept within the above range.
The impurities can be quantified by a known method such as ICP (Inductively Coupled Plasma) emission spectroscopy and atomic absorption spectroscopy.
　また、第１感光層中における、ベンゼン、ホルムアルデヒド、トリクロロエチレン、１，３－ブタジエン、四塩化炭素、クロロホルム、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、ヘキサン等の化合物の含有量が少ないことが好ましい。これら化合物の第１感光層中における含有量としては、質量基準で、１０００ｐｐｍ以下が好ましく、２００ｐｐｍ以下がより好ましく、４０ｐｐｍ以下がさらに好ましい。下限は特に定めるものではないが、現実的に減らせる限界及び測定限界の観点から、質量基準で、１０ｐｐｂ以上とすることができ、１００ｐｐｂ以上とすることができる。
　不純物は、上記の金属の不純物と同様の方法で含有量を抑制することができる。また、公知の測定法により定量することができる。  Further, the content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide and hexane in the first photosensitive layer is small. Is preferred. The content of these compounds in the first photosensitive layer is preferably 1000 ppm or less, more preferably 200 ppm or less, even more preferably 40 ppm or less, on a mass basis. Although the lower limit is not particularly defined, it can be set to 10 ppb or more and 100 ppb or more on a mass basis from the viewpoint of a limit that can be practically reduced and a measurement limit.
The content of the impurities can be suppressed in the same manner as the above-described metal impurities. In addition, it can be quantified by a known measuring method.
　第１感光層の厚みは、２０μｍ以下が好ましく、１５μｍ以下がより好ましく、１２μｍ以下が特に好ましい。第１感光層の厚みが、２０μｍ以下であると、転写フィルム全体の薄膜化、第１感光層又は得られる硬化膜の透過率向上、及び第１感光層又は得られる硬化膜の黄着色化抑制等の点で有利である。
　第１感光層の厚みは、製造適性の観点から、１μｍ以上が好ましく、２μｍ以上がより好ましく、３μｍ以上が特に好ましい。 The thickness of the first photosensitive layer is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 12 μm or less. When the thickness of the first photosensitive layer is 20 μm or less, the entire transfer film is made thinner, the transmittance of the first photosensitive layer or the obtained cured film is improved, and the yellowing of the first photosensitive layer or the obtained cured film is suppressed. And so on.
The thickness of the first photosensitive layer is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably 3 μm or more from the viewpoint of production suitability.
　第１感光層の屈折率としては、１．４７～１．５６が好ましく、１．５０～１．５３がより好ましく、１．５０～１．５２が更に好ましく、１．５１～１．５２が特に好ましい。
　本開示において、「屈折率」は、波長５５０ｎｍにおける屈折率を指す。
　本開示における「屈折率」は、特に断りが無い限り、温度２３℃において波長５５０ｎｍの可視光で、エリプソメトリーによって測定した値を意味する。 The refractive index of the first photosensitive layer is preferably from 1.47 to 1.56, more preferably from 1.50 to 1.53, even more preferably from 1.50 to 1.52, and preferably from 1.51 to 1.52. Particularly preferred.
In the present disclosure, “refractive index” refers to a refractive index at a wavelength of 550 nm.
The “refractive index” in the present disclosure means a value measured by ellipsometry with visible light having a wavelength of 550 nm at a temperature of 23 ° C., unless otherwise specified.
～第１感光層の形成～
　第１感光層の形成方法には、特に限定はなく、公知の方法を用いることができる。
　第１感光層の形成方法の一例としては、仮支持体上に、溶剤を含有する第１感光層形成用の組成物（第１感光層用組成物）を塗布等の方法で付与し、必要に応じて乾燥させることによって形成する方法が挙げられる。
　第１感光層用組成物は、少なくとも、バインダーポリマー、重合性化合物、光重合開始剤及び溶剤（特に有機溶剤）、並びに必要に応じて界面活性剤、及び添加剤等の他の成分を混合することにより調製することができる。 ~ Formation of the first photosensitive layer ~
The method for forming the first photosensitive layer is not particularly limited, and a known method can be used.
As an example of a method for forming the first photosensitive layer, a composition for forming a first photosensitive layer (a composition for a first photosensitive layer) containing a solvent is applied onto a temporary support by a method such as coating, and the method is applied. And a method of forming by drying.
The composition for the first photosensitive layer mixes at least other components such as a binder polymer, a polymerizable compound, a photopolymerization initiator and a solvent (particularly an organic solvent), and, if necessary, a surfactant and an additive. Can be prepared.
　塗布の方法としては、公知の方法を用いることができ、例えば、印刷法、スプレー法、ロールコート法、バーコート法、カーテンコート法、スピンコート法、ダイコート法（即ち、スリットコート法）等が挙げられ、ダイコート法が好ましい。
　乾燥の方法としては、自然乾燥、加熱乾燥、減圧乾燥等の公知の方法を、単独で又は複数組み合わせて適用することができる。 A known method can be used as a coating method, and examples thereof include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method). And a die coating method is preferred.
As a drying method, known methods such as natural drying, heat drying, and drying under reduced pressure can be applied alone or in combination.
　第１感光層用組成物に用いられる溶剤としては、通常用いられる溶剤を特に制限なく用いることができる。溶剤としては、有機溶剤が好ましい。
　有機溶剤としては、例えば、メチルエチルケトン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート（別名：１－メトキシ－２－プロピルアセテート）、ジエチレングリコールエチルメチルエーテル、シクロヘキサノン、メチルイソブチルケトン、乳酸エチル、乳酸メチル、カプロラクタム、ｎ－プロパノール、２－プロパノールなどを挙げることができる。
　また、溶剤は、二種類以上の有機溶剤を混合した混合溶剤として用いてもよい。
　混合溶剤としては、メチルエチルケトンとプロピレングリコールモノメチルエーテルアセテートとの混合溶剤、又はジエチレングリコールエチルメチルエーテルとプロピレングリコールモノメチルエーテルアセテートとの混合溶剤が好ましい。 As the solvent used in the composition for the first photosensitive layer, a commonly used solvent can be used without any particular limitation. As the solvent, an organic solvent is preferable.
Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (alias: 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam , N-propanol, 2-propanol and the like.
Further, the solvent may be used as a mixed solvent obtained by mixing two or more kinds of organic solvents.
As the mixed solvent, a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate, or a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate is preferable.
　溶剤を用いる場合、第１感光層用組成物の固形分量は、第１感光層用組成物の全量に対して、５質量％～８０質量％が好ましく、５質量％～４０質量％がより好ましく、５質量％～３０質量％が特に好ましい。 When a solvent is used, the solid content of the composition for the first photosensitive layer is preferably 5% by mass to 80% by mass, more preferably 5% by mass to 40% by mass, based on the total amount of the composition for the first photosensitive layer. 5% to 30% by mass is particularly preferred.
　また、溶剤を用いる場合、第１感光層用組成物の粘度（２５℃）は、塗布性の観点から、１ｍＰａ・ｓ～５０ｍＰａ・ｓが好ましく、２ｍＰａ・ｓ～４０ｍＰａ・ｓがより好ましく、３ｍＰａ・ｓ～３０ｍＰａ・ｓが更に好ましい。
　粘度は、例えば、ＶＩＳＣＯＭＥＴＥＲ ＴＶ－２２（東機産業（株）製）を用いて測定される値である。
　第１感光層用組成物が溶剤を含有する場合、第１感光層用組成物の表面張力（２５℃）は、塗布性の観点から、５ｍＮ／ｍ～１００ｍＮ／ｍが好ましく、１０ｍＮ／ｍ～８０ｍＮ／ｍがより好ましく、１５ｍＮ／ｍ～４０ｍＮ／ｍが特に好ましい。
　表面張力は、例えば、Ａｕｔｏｍａｔｉｃ　Ｓｕｒｆａｃｅ　Ｔｅｎｓｉｏｍｅｔｅｒ　ＣＢＶＰ-Ｚ（協和界面科学（株）製）を用いて測定される値である。 When a solvent is used, the viscosity (25 ° C.) of the composition for the first photosensitive layer is preferably from 1 mPa · s to 50 mPa · s, more preferably from 2 mPa · s to 40 mPa · s, and preferably from 3 mPa · s, from the viewpoint of applicability. S to 30 mPa · s is more preferable.
The viscosity is a value measured using, for example, VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.).
When the composition for the first photosensitive layer contains a solvent, the surface tension (25 ° C.) of the composition for the first photosensitive layer is preferably from 5 mN / m to 100 mN / m from the viewpoint of applicability, and is preferably from 10 mN / m to 10 mN / m. 80 mN / m is more preferable, and 15 mN / m to 40 mN / m is particularly preferable.
The surface tension is a value measured by using, for example, an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).
　溶剤としては、米国特許出願公開第２００５／２８２０７３号明細書の段落００５４及び００５５に記載のＳｏｌｖｅｎｔを用いることもでき、この明細書の内容は本明細書に組み込まれる。
　また、溶剤として、必要に応じて沸点が１８０℃～２５０℃である有機溶剤（高沸点溶剤）を使用することもできる。 Solvents described in paragraphs 0054 and 0055 of US Patent Application Publication No. 2005/282073 can also be used as the solvent, the contents of which are incorporated herein.
Further, as the solvent, an organic solvent having a boiling point of 180 ° C. to 250 ° C. (high boiling point solvent) can be used as necessary.
（遮光層）
　遮光層は、第１感光層の仮支持体を有する側とは反対側に配置された光遮断性を有する層であり、少なくともバインダーポリマーを含み、かつ、光学濃度を０．５以上として形成されたものである。遮光層は、バインダーポリマーのほか、紫外線吸収材料を含むことが好ましく、必要に応じて、硬化成分を含んでいてもよく、界面活性剤、溶剤、及び添加剤等の他の成分を含んでいてもよい。
　硬化成分としては、重合性化合物及び光重合開始剤等が含まれる。 (Light shielding layer)
The light-shielding layer is a layer having a light-blocking property arranged on the side opposite to the side having the temporary support of the first photosensitive layer, contains at least a binder polymer, and is formed with an optical density of 0.5 or more. It is a thing. The light-shielding layer preferably contains, in addition to the binder polymer, an ultraviolet absorbing material.If necessary, the light-shielding layer may contain a curing component, and may contain other components such as a surfactant, a solvent, and an additive. Is also good.
The curing component includes a polymerizable compound, a photopolymerization initiator, and the like.
　遮光層は、光学濃度を０．５以上とされている。
　光学濃度が０．５以上であることで、広い波長領域に亘る光を吸収しやすく、遮光層の一方の側から他方の側に透過する光の透過量を小さく抑えることができる。これにより、透明基材の一方の側に配された感光層への他方の側からの光の影響を低減できる。
　上記の観点から、光学濃度は高いほど好ましく、１．５以上が好ましく、２．０以上がより好ましく、２．５以上がさらに好ましく、３．０以上が更に好ましい。
　光学濃度の上限を定めるものではないが、遮光層の処方設計の容易さ等の観点から、光学濃度は例えば６．０以下又は５．０以下とすることができる。 The light shielding layer has an optical density of 0.5 or more.
When the optical density is 0.5 or more, light over a wide wavelength range is easily absorbed, and the amount of light transmitted from one side of the light-shielding layer to the other side can be reduced. Thereby, the influence of light from the other side on the photosensitive layer disposed on one side of the transparent substrate can be reduced.
In light of the above, the higher the optical density, the more preferable it is.
Although the upper limit of the optical density is not determined, the optical density can be set to, for example, 6.0 or less or 5.0 or less from the viewpoint of easy design of the prescription of the light shielding layer.
　本開示における光学濃度は、仮支持体／遮光層／ガラス基材の積層構造を有する積層体を作製し、積層体の光学濃度を透過濃度計（ＢＭＴ－１、サカタインクスエンジニアリング社製）を用いて測定する。また、積層体に使用した仮支持体及びガラス基材の光学濃度を同様の方法で測定する。そして、積層体の光学濃度から仮支持体及びガラス基材の光学濃度を減算し、遮光層の光学濃度とする。 In the present disclosure, the optical density is measured by preparing a laminate having a laminated structure of a temporary support / light-shielding layer / glass substrate, and measuring the optical density of the laminate using a transmission densitometer (BMT-1, manufactured by Sakata Inx Engineering). Measure. The optical density of the temporary support and the glass substrate used for the laminate is measured by the same method. Then, the optical density of the temporary support and the glass substrate is subtracted from the optical density of the laminate to obtain the optical density of the light-shielding layer.
－バインダーポリマー－
　遮光層は、バインダーポリマーの少なくとも一種を含有する。
　バインダーポリマーは、アルカリ性溶媒との接触により溶解しうる樹脂（いわゆるアルカリ可溶性樹脂）であることが好ましい。 -Binder polymer-
The light-shielding layer contains at least one binder polymer.
The binder polymer is preferably a resin that can be dissolved by contact with an alkaline solvent (so-called alkali-soluble resin).
　バインダーポリマーとしては、例えば、特開２０１１－９５７１６号公報の段落００２５、特開２０１０－２３７５８９号公報の段落００３３～００５２に記載された樹脂を挙げることができる。 Examples of the binder polymer include resins described in paragraph 0025 of JP-A-2011-95716 and paragraphs 0033 to 0052 of JP-A-2010-237589.
　遮光層は、パターン形成性がより良好となる観点から、カルボキシ基を有するバインダーポリマーを含有することが好ましく、酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基含有アクリル樹脂を含有することが特に好ましい。
　バインダーポリマーの酸価は、６０ｍｇＫＯＨ／ｇ以上２５０ｍｇＫＯＨ／ｇ以下が好ましく、７０ｍｇＫＯＨ／ｇ以上１８０ｍｇＫＯＨ／ｇ以下が好ましい。
　カルボキシ基を有するバインダーポリマーを含有することで、形成されるパターン端部の直線性がより良好となり、所謂エッジラフネスが良化する傾向がある。
　なお、エッジラフネスとは、パターン端部をレーザー顕微鏡（例えば、ＶＫ－９５００、キーエンス（株）、対物レンズ５０倍）を用いて観察し、視野内のパターン端部のうち、最も膨らんだ箇所（山頂部）と最もくびれた箇所（谷底部）との差を絶対値として、異なる５箇所について絶対値を求め、５箇所の平均値を算出し、算出した値を意味する。 The light-shielding layer preferably contains a binder polymer having a carboxy group, and particularly preferably contains a carboxy-group-containing acrylic resin having an acid value of 60 mgKOH / g or more, from the viewpoint of better pattern formability.
The acid value of the binder polymer is preferably from 60 mgKOH / g to 250 mgKOH / g, and more preferably from 70 mgKOH / g to 180 mgKOH / g.
By containing a binder polymer having a carboxy group, the linearity of the formed pattern end becomes better, and so-called edge roughness tends to be improved.
The edge roughness refers to an edge of a pattern observed using a laser microscope (for example, VK-9500, Keyence Corporation, objective lens 50 times), and the most swelled portion of the pattern edge in the field of view ( With the difference between the peak (top of the mountain) and the most constricted portion (bottom of the valley) as the absolute value, the absolute value is determined for five different locations, the average value of the five locations is calculated, and the calculated value is meant.
　バインダーポリマーの具体的な例としては、ベンジル（メタ）アクリレート／（メタ）アクリル酸のランダム共重合体、スチレン／（メタ）アクリル酸のランダム共重合体、シクロヘキシル（メタ）アクリレート／（メタ）アクリル酸／メチル（メタ）アクリレートの共重合体、シクロヘキシル（メタ）アクリレート／メチル（メタ）アクリレート／（メタ）アクリル酸の共重合体のグリシジル（メタ）アクリレート付加物、ベンジル（メタ）アクリレート／（メタ）アクリル酸の共重合体のグリシジル（メタ）アクリレート付加物、アリル（メタ）アクリレート／（メタ）アクリル酸の共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸／ヒドロキシエチル（メタ）アクリレートの共重合体などが挙げられる。
　中でも、現像性の観点から、ベンジル（メタ）アクリレート／（メタ）アクリル酸のランダム共重合体が好ましい。 Specific examples of the binder polymer include a random copolymer of benzyl (meth) acrylate / (meth) acrylic acid, a random copolymer of styrene / (meth) acrylic acid, and cyclohexyl (meth) acrylate / (meth) acrylic. Acid / methyl (meth) acrylate copolymer, cyclohexyl (meth) acrylate / methyl (meth) acrylate / (meth) acrylic acid copolymer glycidyl (meth) acrylate adduct, benzyl (meth) acrylate / (meth) A) glycidyl (meth) acrylate adduct of acrylic acid copolymer, allyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / hydroxyethyl (meth) acrylate And the like.
Among them, a random copolymer of benzyl (meth) acrylate / (meth) acrylic acid is preferred from the viewpoint of developability.
　バインダーポリマーは、上市されている市販品を用いてもよく、例えば、藤倉化成株式会社のアクリベース（登録商標）ＦＦＳ－６０５８、ＦＦ１８７、大成ファインケミカル株式会社のアクリット（登録商標）８ＫＢ－００１等の８ＫＢシリーズが挙げられる。 As the binder polymer, commercially available products may be used. For example, Acrybase (registered trademark) FFS-6058 and FF187 of Fujikura Kasei Co., Ltd., and Acryt (registered trademark) 8KB-001 of Taisei Fine Chemical Co., Ltd. may be used. 8KB series.
　バインダーポリマーの重量平均分子量（Ｍｗ）としては、４０００～２５０００が好ましく、４０００～２００００がより好ましく、５０００～１８０００が更に好ましい。
　バインダーポリマーの重量平均分子量が４０００以上であると、第１感光層の現像時における除去性が良好となる。更には、形成されるパターンのタック性が抑制されるため、転写フィルムが保護フィルムを有する場合、保護フィルムを剥離する際の保護フィルムの剥離性が向上する。一方、バインダーポリマーの重量平均分子量が２５０００以下であると、熱垂れ性が向上し、かつ、現像残渣の発生が抑制される。 The weight average molecular weight (Mw) of the binder polymer is preferably from 4,000 to 25,000, more preferably from 4,000 to 20,000, still more preferably from 5,000 to 18,000.
When the weight average molecular weight of the binder polymer is 4000 or more, the removability of the first photosensitive layer during development becomes good. Furthermore, since the tackiness of the formed pattern is suppressed, when the transfer film has a protective film, the peelability of the protective film when peeling off the protective film is improved. On the other hand, when the weight average molecular weight of the binder polymer is 25,000 or less, the heat sagging property is improved, and the generation of development residues is suppressed.
　バインダーポリマーの重量平均分子量の測定は、下記の条件にて、ゲル透過クロマトグラフ（ＧＰＣ）により行うことができる。検量線は、東ソー（株）製「標準試料ＴＳＫ　ｓｔａｎｄａｒｄ，ｐｏｌｙｓｔｙｒｅｎｅ」：「Ｆ－４０」、「Ｆ－２０」、「Ｆ－４」、「Ｆ－１」、「Ａ－５０００」、「Ａ－２５００」、「Ａ－１０００」、「ｎ－プロピルベンゼン」の８サンプルから作製する。
　<条件>
・ＧＰＣ：ＨＬＣ（登録商標）－８０２０ＧＰＣ（東ソー（株）製）
・カラム：ＴＳＫｇｅｌ（登録商標）、Ｓｕｐｅｒ　ＭｕｌｔｉｐｏｒｅＨＺ－Ｈ（東ソー（株）製、４．６ｍｍＩＤ×１５ｃｍ）を３本
・溶離液：ＴＨＦ（テトラヒドロフラン）
・試料濃度：０．４５質量％
・流速：０．３５ｍｌ／ｍｉｎ
・サンプル注入量：１０μｌ
・測定温度：４０℃
・検出器：示差屈折計（ＲＩ） The weight average molecular weight of the binder polymer can be measured by gel permeation chromatography (GPC) under the following conditions. The calibration curve is "Standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", "A -2500 "," A-1000 ", and" n-propylbenzene ".
<Condition>
GPC: HLC (registered trademark) -8020GPC (manufactured by Tosoh Corporation)
-Column: TSKgel (registered trademark), 3 pieces of Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm)-Eluent: THF (tetrahydrofuran)
-Sample concentration: 0.45% by mass
・ Flow rate: 0.35 ml / min
・ Sample injection volume: 10 μl
・ Measurement temperature: 40 ° C
・ Detector: Differential refractometer (RI)
　なお、バインダーポリマーの酸価は、ＪＩＳ　Ｋ００７０（１９９２年）に記載の方法に準拠して求められる値である。 The acid value of the binder polymer is a value determined according to the method described in JIS K0070 (1992).
　遮光層におけるバインダーポリマーの含有量は、遮光層の全固形分量に対し、１０質量％～７０質量％が好ましく、１５質量％～６０質量％がより好ましく、２０質量％～５０質量％がさらに好ましい。 The content of the binder polymer in the light-shielding layer is preferably from 10% by mass to 70% by mass, more preferably from 15% by mass to 60% by mass, and still more preferably from 20% by mass to 50% by mass, based on the total solid content of the light-shielding layer. .
－紫外線吸収材料－
　遮光層は、更に、紫外線吸収材料の少なくとも一種を含むことが好ましい。
　ここでの紫外線とは、波長２５０ｎｍ～４００ｎｍの範囲の光を指す。
　紫外線吸収材料としては、紫外線に吸収性を有する材料であれば制限はなく、例えば、顔料（特に黒色顔料）、２５０ｎｍ～４００ｎｍの間に吸収極大を有する紫外線吸収剤と称される材料等が挙げられる。 -UV absorbing material-
It is preferable that the light shielding layer further contains at least one kind of ultraviolet absorbing material.
Here, the ultraviolet light refers to light having a wavelength in the range of 250 nm to 400 nm.
The ultraviolet absorbing material is not limited as long as it has a property of absorbing ultraviolet rays, and examples thereof include pigments (especially black pigments) and materials called ultraviolet absorbers having an absorption maximum between 250 nm and 400 nm. Can be
（黒色顔料）
　黒色顔料は、遮光層における遮光性を発現しうる限り特に制限はない。
　黒色顔料としては、公知の黒色顔料、例えば、有機顔料、及び無機顔料から選ばれる黒色顔料を好適に用いることができる。無機顔料は金属顔料、金属酸化物顔料などの金属化合物を含む顔料を包含する。
　形成される遮光層の光学濃度が良好であるという観点から、黒色顔料としては、例えば、カーボンブラック、チタンカーボン、酸化鉄、チタンブラックなどの酸化チタン顔料、黒鉛などが挙げられる。 (Black pigment)
The black pigment is not particularly limited as long as it can exhibit light-shielding properties in the light-shielding layer.
As the black pigment, a known black pigment, for example, a black pigment selected from organic pigments and inorganic pigments can be suitably used. Inorganic pigments include pigments containing metal compounds such as metal pigments and metal oxide pigments.
From the viewpoint that the optical density of the formed light-shielding layer is good, examples of the black pigment include titanium oxide pigments such as carbon black, titanium carbon, iron oxide, and titanium black, and graphite.
　本開示における遮光層は、紫外線吸収材料としてカーボンブラックを含む態様が好ましい。
　カーボンブラックは、市販品としても入手可能であり、例えば、東京インキ社製の黒顔料分散物　ＦＤＫ－９１１〔商品名：ＦＤＫ－９１１〕などが挙げられる。
　カーボンブラックは、遮光層におけるカーボンブラックの均一分散性がより良好となるという点で、表面が樹脂で被覆されたカーボンブラック（以下、樹脂被覆カーボンブラックともいう。）であることが好ましい。なお、樹脂によるカーボンブラックの被覆は、カーボンブラックの表面の少なくとも一部が被覆されていればよく、表面全体が被覆されていてもよい。
　樹脂被覆カーボンブラックは、例えば、特許第５３２０６５２号公報の段落００３６～００４２に記載の方法で作製することができる。また、市販品としても入手可能であり、例えば、山陽色素社製のＳＦ　Ｂｌａｃｋ　ＧＢ４０５１などが挙げられる。 An embodiment in which the light-shielding layer according to the present disclosure includes carbon black as the ultraviolet absorbing material is preferable.
Carbon black is also available as a commercial product, and examples thereof include a black pigment dispersion FDK-911 [trade name: FDK-911] manufactured by Tokyo Ink.
The carbon black is preferably a carbon black whose surface is coated with a resin (hereinafter, also referred to as a resin-coated carbon black) from the viewpoint that the uniform dispersibility of the carbon black in the light-shielding layer becomes better. The resin may be coated with the carbon black as long as at least a part of the surface of the carbon black is coated, and the entire surface may be coated.
The resin-coated carbon black can be produced, for example, by the method described in paragraphs 0036 to 0042 of Japanese Patent No. 5320652. It is also available as a commercial product, for example, SF Black GB4051 manufactured by Sanyo Dyeing Co., Ltd. and the like.
　黒色顔料の粒径は、分散安定性の観点から、数平均粒径で０．００１μｍ～０．３μｍが好ましく、０．０１μｍ～０．２μｍがより好ましい。
　「粒径」とは粒子の電子顕微鏡写真画像を同面積の円とした時の直径を指し、また「数平均粒径」とは、任意の１００個の粒子について粒径を求め、この粒径の平均値をいう。
　なお、遮光層に含有される黒色顔料の数平均粒径は、黒色顔料を含む遮光層を透過型電子顕微鏡（ＪＥＯＬ）により、３００，０００倍で撮影した写真を用いて、視野角に含まれる任意の１００個の粒子について、粒子径を測定し、測定した値の平均値として算出することができる。 The particle diameter of the black pigment is preferably from 0.001 μm to 0.3 μm, more preferably from 0.01 μm to 0.2 μm in terms of number average particle diameter from the viewpoint of dispersion stability.
The “particle size” refers to the diameter of an electron micrograph image of a particle when it is formed into a circle of the same area, and the “number average particle size” refers to the particle size of any 100 particles, Mean.
The number average particle diameter of the black pigment contained in the light-shielding layer is included in the viewing angle by using a photograph of the light-shielding layer containing the black pigment taken at a magnification of 300,000 with a transmission electron microscope (JEOL). The particle diameter of any 100 particles can be measured and calculated as the average of the measured values.
（黒色以外の顔料）
　黒色以外の顔料としては、例えば、特開２００８－２２４９８２号公報段落００３０～００４４に記載の顔料であって黒色以外の色相を呈する顔料、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　５８、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　７９のクロロ基（Ｃｌ）を水酸基（ＯＨ）に変更した顔料などが挙げられる。 (Pigments other than black)
Examples of the non-black pigment include pigments described in JP-A-2008-224982, paragraphs 0030 to 0044, which exhibit a hue other than black; I. Pigment Green 58, C.I. I. Pigment Blue 79 in which the chloro group (Cl) is changed to a hydroxyl group (OH).
　中でも、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１１、２４、１０８、１０９、１１０、１３８、１３９、１５０、１５１、１５４、１６７、１８０、１８５；Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　３６、３８、６２、６４；Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１２２、１５０、１７１、１７５、１７７、２０９、２２４、２４２、２５４、２５５；Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　１９、２３、２９、３２；Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：１、１５：３、１５：６、１６、２２、６０、６６；Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　７、３６、３７、及び５８が好ましい。但し、遮光層が含むことができる顔料は、上記の顔料に限定されるものではない。 Among them, C.I. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185; I. Pigment Orange 36, 38, 62, 64; C.I. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255; I. Pigment Violet 19, 23, 29, 32; I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66; I. Pigment Green 7, 36, 37, and 58 are preferred. However, the pigment that can be included in the light-shielding layer is not limited to the above pigment.
　また、２５０ｎｍ～４００ｎｍの間に吸収極大を有する紫外線吸収剤の具体例としては、スミソーブ１３０（住友化学社製）、ＥＶＥＲＳＯＲＢ１０、ＥＶＥＲＳＯＲＢ１１、ＥＶＥＲＳＯＲＢ１２（以上、台湾永光化学工業社製）、トミソーブ８００（エーピーアイコーポレーション社製）、ＳＥＥＳＯＲＢ１００、ＳＥＥＳＯＲＢ１０１、ＳＥＥＳＯＲＢ１０１Ｓ、ＳＥＥＳＯＲＢ１０２、ＳＥＥＳＯＲＢ１０３、ＳＥＥＳＯＲＢ１０５、ＳＥＥＳＯＲＢ１０６、ＳＥＥＳＯＲＢ１０７、ＳＥＥＳＯＲＢ１５１（以上、シプロ化成社製）などのベンゾフェノン化合物；スミソーブ２００、スミソーブ２５０、スミソーブ３００、スミソーブ３４０、スミソーブ３５０（以上、住友化学社製）、ＪＦ７７、ＪＦ７８、ＪＦ７９、ＪＦ８０、ＪＦ８３（以上、城北化学工業社製）、ＴＩＮＵＶＩＮ ＰＳ、ＴＩＮＵＶＩＮ９９－２、ＴＩＮＵＶＩＮ１０９、ＴＩＮＵＶＩＮ３８４－２、ＴＩＮＵＶＩＮ９００、ＴＩＮＵＶＩＮ９２８、ＴＩＮＵＶＩＮ１１３０（以上、ＢＡＳＦ社製）、ＥＶＥＲＳＯＲＢ７０、ＥＶＥＲＳＯＲＢ７１、ＥＶＥＲＳＯＲＢ７２、ＥＶＥＲＳＯＲＢ７３、ＥＶＥＲＳＯＲＢ７４、ＥＶＥＲＳＯＲＢ７５、ＥＶＥＲＳＯＲＢ７６、ＥＶＥＲＳＯＲＢ２３４、ＥＶＥＲＳＯＲＢ７７、ＥＶＥＲＳＯＲＢ７８、ＥＶＥＲＳＯＲＢ８０、ＥＶＥＲＳＯＲＢ８１（以上、台湾永光化学工業社製）、トミソーブ１００、トミソーブ６００（以上、エーピーアイコーポレーション社製）、ＳＥＥＳＯＲＢ７０１、ＳＥＥＳＯＲＢ７０２、ＳＥＥＳＯＲＢ７０３、ＳＥＥＳＯＲＢ７０４、ＳＥＥＳＯＲＢ７０６、ＳＥＥＳＯＲＢ７０７、ＳＥＥＳＯＲＢ７０９（以上、シプロ化成社製）などのベンゾトリアゾール化合物；スミソーブ４００（住友化学社製）、サリチル酸フェニルなどのベンゾエート化合物；ＴＩＮＵＶＩＮ４００、ＴＩＮＵＶＩＮ４０５、ＴＩＮＵＶＩＮ４６０、ＴＩＮＵＶＩＮ４７７ＤＷ、ＴＩＮＵＶＩＮ４７９（以上、ＢＡＳＦ社製）などのヒドロキシフェニルトリアジン化合物；などを挙げることができる。 Specific examples of the UV absorber having an absorption maximum between 250 nm and 400 nm include Sumisorb 130 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (all manufactured by Taiwan Eiko Chemical Co., Ltd.), and Tomissorb 800 (AP Benzophenone compounds such as SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by Cipro Kasei Co., Ltd.); (The above are manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80 JF83 (all manufactured by Johoku Chemical Industry Co., Ltd.), TINUVIN @ PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN900, TINUVIN928, TINUVIN1130 (all manufactured by BASF), EVERSORB70, EVERSOBER71BERVERBER72RVERVERBERVERBER72RVERVERBERVERSERVERBERVERBER72RVERBERVERS EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (all manufactured by Taiwan Eiko Chemical Co., Ltd.), Tomisorb 100, Tomisorb 600 (all manufactured by API Corporation), SEESORB701, SEESORB702, SESEORB70 Benzotriazole compounds such as SORB704, SEESORB706, SEESORB707, and SEESORB709 (all manufactured by Cipro Kasei); benzoate compounds such as Sumisorb 400 (manufactured by Sumitomo Chemical Co., Ltd.) and phenyl salicylate; Hydroxyphenyltriazine compound; and the like.
　遮光層における紫外線吸収材料の含有量（遮光層が黒色顔料のみを含む場合は、黒色顔料の含有量、黒色顔料と黒色以外の顔料を含む場合は両者の合計質量）は、遮光層の全固形分量に対して、１０質量％～７０質量％であることが好ましく、２０質量％～６０質量％であることがより好ましく、２０質量％～４５質量％であることがさらに好ましい。
　紫外線吸収材料の含有量が１０質量％以上であると、膜厚を薄く保ったまま遮光層の光学濃度を高めることができる。紫外線吸収材料の含有量が７０質量％以下であると、遮光層をパターニングする際の硬化感度が良好となる。 The content of the ultraviolet absorbing material in the light-shielding layer (the content of the black pigment when the light-shielding layer contains only a black pigment, and the total mass of the black pigment and the pigment other than black when the light-shielding layer contains only a black pigment) is determined by the total solid content of the light-shielding layer. The amount is preferably from 10% by mass to 70% by mass, more preferably from 20% by mass to 60% by mass, and still more preferably from 20% by mass to 45% by mass, based on the amount.
When the content of the ultraviolet absorbing material is 10% by mass or more, the optical density of the light shielding layer can be increased while keeping the film thickness small. When the content of the ultraviolet absorbing material is 70% by mass or less, the curing sensitivity at the time of patterning the light shielding layer becomes good.
－重合性化合物－
　遮光層は、更に硬化成分として、重合性化合物の少なくとも一種を含むことが好ましい。遮光層が、重合性化合物を含有すると、現像時における溶解性に優れたものとなる。重合性化合物は、分子中に少なくとも１個の重合性基を有する化合物であり、単量体又は重合体のいずれも挙げられるが、現像時の溶解性の点で単量体（即ち、重合性モノマー）がより好ましい。重合性基の種類には、特に制限はない。 -Polymerizable compound-
The light-shielding layer preferably further contains at least one polymerizable compound as a curing component. If the light-shielding layer contains a polymerizable compound, the solubility at the time of development will be excellent. The polymerizable compound is a compound having at least one polymerizable group in a molecule, and may be either a monomer or a polymer. Monomer) is more preferred. There is no particular limitation on the type of the polymerizable group.
　重合性基としては、エチレン性不飽和基、及びエポキシ基などが挙げられ、エチレン性不飽和基が好ましく、（メタ）アクリロイル基がより好ましい。 (4) Examples of the polymerizable group include an ethylenically unsaturated group and an epoxy group. An ethylenically unsaturated group is preferable, and a (meth) acryloyl group is more preferable.
　重合性化合物は、重合性基を２個以上有している、２官能以上（多官能）の重合性モノマーであることが好ましく、２官能の重合性モノマーであることがより好ましい。多官能の重合性モノマーを用いることで、遮光層を現像する際の現像残渣の発生を抑制することができる。２官能の重合性モノマーを用いることで、弱アルカリ現像液（例えば、炭酸ナトリウム水溶液）における現像においても、現像残渣の発生を抑制することができる。 (4) The polymerizable compound is preferably a bifunctional or higher (polyfunctional) polymerizable monomer having two or more polymerizable groups, and more preferably a bifunctional polymerizable monomer. By using a polyfunctional polymerizable monomer, generation of a development residue when developing the light shielding layer can be suppressed. By using a bifunctional polymerizable monomer, generation of a development residue can be suppressed even in development with a weak alkaline developer (for example, an aqueous solution of sodium carbonate).
　重合性化合物としては、例えば、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート及びフェノキシエチル（メタ）アクリレートなどの単官能アクリレート又は単官能メタクリレート；ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、トリメチロールエタントリアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパンジアクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリ（アクリロイルオキシエチル）イソシアヌレート、トリ（アクリロイルオキシエチル）シアヌレート、グリセリントリ（メタ）アクリレート；トリメチロールプロパン又はグリセリン等の多官能アルコールにエチレンオキシド又はプロピレンオキシドを付加した後（メタ）アクリレート化したもの等の多官能アクリレートや多官能メタクリレートを挙げることができる。
　また、ウレタン（メタ）アクリレート化合物などのウレタン系モノマーも好ましく用いることができる Examples of the polymerizable compound include monofunctional acrylates or monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, Xanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; trimethylolpropane or glycerin Examples thereof include polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated.
Further, urethane monomers such as urethane (meth) acrylate compounds can also be preferably used.
　さらに特公昭４８－４１７０８号公報、特公昭５０－６０３４号公報及び特開昭５１－３７１９３号公報に記載のウレタンアクリレート；特開昭４８－６４１８３号公報、特公昭４９－４３１９１号公報及び特公昭５２－３０４９０号公報に記載のポリエステルアクリレート；エポキシ樹脂と（メタ）アクリル酸の反応生成物であるエポキシアクリレート等の多官能アクリレート又はメタクリレートが挙げられる。
　層の曲げ性の観点から、ウレタン（メタ）アクリレート化合物が好ましい。 Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 and JP-B-49-43191. Polyester acrylates described in JP-A-52-30490; polyfunctional acrylates or methacrylates such as epoxy acrylate which is a reaction product of an epoxy resin and (meth) acrylic acid.
A urethane (meth) acrylate compound is preferred from the viewpoint of layer flexibility.
　重合性化合物は、上市されている市販品を用いてもよい。
　市販品としては、例えば、トリシクロデカンジメタノールジアクリレート（Ａ－ＤＣＰ、新中村化学工業（株）、２官能、分子量３０４）、トリシクロデカンジメナノールジメタクリレート（ＤＣＰ、新中村化学工業（株）、２官能、分子量３３２）、１，９－ノナンジオールジアクリレート（Ａ－ＮＯＤ－Ｎ、新中村化学工業（株）、２官能、分子量２６８）、１，６－ヘキサンジオールジアクリレート（Ａ－ＨＤ－Ｎ、新中村化学工業（株）、２官能、分子量２２６）、９，９－ビス［４－（２－アクリロイルオキシエトキシ）フェニル］フルオレン（Ａ－ＢＰＥＦ、新中村化学工業（株）、２官能、分子量５４６）、ウレタンアクリレート（ＵＡ－１６０ＴＭ、新中村化学工業（株）、２官能、分子量１６００）、１，６－ヘキサンジオールジアクリレート（Ｖ＃２３０、大阪有機化学工業（株）、２官能、分子量２２６）、１，３－アダマンチルジアクリレート（ＡＤＤＡ、三菱ガス化学（株）、２官能、分子量２７６）、トリメチロールプロパントリアクリレート（Ａ－ＴＭＰＴ、新中村化学工業（株）、３官能、分子量２９６）、トリメチロールプロパンエチレンオキサイド（ＥＯ）変性（ｎ≒１）トリアクリレート（Ｍ－３５０、東亞合成（株）、３官能）、ペンタエリスリトールテトラアクリレート（Ａ－ＴＭＭＴ、新中村化学工業（株）、４官能、分子量３５２）、ジペンタエリスリトールヘキサアクリレート（Ａ－ＤＰＨ、新中村化学工業（株）、６官能、分子量５７８）、ペンタエリスリトールトリアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー（ＵＡ－３０６Ｈ、共栄社化学（株）、６官能）、ペンタエリスリトールトリアクリレートトルエンジイソシアネートウレタンプレポリマー（ＵＡ３０６Ｔ、共栄社化学（株）、６官能）、ジペンタエリスリトールヘキサアクリレート（ＫＡＹＡＲＡＤ　ＤＰＨＡ、日本化薬（株）、６官能、分子量５７９）、ウレタンアクリレート（ＵＡ－３２Ｐ、新中村化学工業（株）、９官能）、ウレタンアクリレート（８ＵＸ－０１５Ａ、大成ファインケミカル（株）、１５官能）などが好ましく挙げられる。 As the polymerizable compound, commercially available products may be used.
Examples of commercially available products include tricyclodecane dimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Co., Ltd., bifunctional, molecular weight 304), tricyclodecane dimenanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., Ltd.) Co., Ltd., bifunctional, molecular weight 332), 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd., bifunctional, molecular weight 268), 1,6-hexanediol diacrylate (A -HD-N, Shin-Nakamura Chemical Co., Ltd., bifunctional, molecular weight 226), 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (A-BPEF, Shin-Nakamura Chemical Co., Ltd.) Bifunctional, molecular weight 546), urethane acrylate (UA-160TM, Shin-Nakamura Chemical Co., Ltd., bifunctional, molecular weight 1600), 1,6-hexanedi Diacrylate (V # 230, Osaka Organic Chemical Industry Co., Ltd., bifunctional, molecular weight 226), 1,3-adamantyl diacrylate (ADDA, Mitsubishi Gas Chemical Co., Ltd., bifunctional, molecular weight 276), trimethylolpropane Triacrylate (A-TMPT, Shin-Nakamura Chemical Co., Ltd., trifunctional, molecular weight 296), trimethylolpropane ethylene oxide (EO) -modified (n ≒ 1) triacrylate (M-350, Toagosei Co., Ltd., 3 Pentaerythritol tetraacrylate (A-TMMT, Shin-Nakamura Chemical Co., Ltd., 4-functional, molecular weight 352), dipentaerythritol hexaacrylate (A-DPH, Shin-Nakamura Chemical Co., Ltd.), 6-functional, molecular weight 578 ), Pentaerythritol triacrylate hexamethylene diisocyanate urethane Polymer (UA-306H, Kyoeisha Chemical Co., Ltd., hexafunctional), pentaerythritol triacrylate toluene diisocyanate urethane prepolymer (UA306T, Kyoeisha Chemical Co., Ltd., hexafunctional), dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku) Preferred are urethane acrylate (UA-32P, Shin-Nakamura Chemical Co., Ltd., 9-functional), urethane acrylate (8UX-015A, Taisei Fine Chemical Co., Ltd., 15-functional), etc. Can be
　重合性化合物は、分子量が３０００以下であることが好ましく、２０００以下であることがより好ましく、１０００以下あることがさらに好ましく、５００以下であることが特に好ましい。
　重合性化合物の分子量が５００以下であると、低温での熱処理における熱だれが起きやすい。特に、分子量５００以下の２官能の重合性モノマーが好ましい。 The molecular weight of the polymerizable compound is preferably 3,000 or less, more preferably 2,000 or less, further preferably 1,000 or less, and particularly preferably 500 or less.
When the molecular weight of the polymerizable compound is 500 or less, heat dripping is likely to occur in heat treatment at a low temperature. Particularly, a bifunctional polymerizable monomer having a molecular weight of 500 or less is preferable.
　重合性化合物の分子量は、質量分析（例えば、液体クロマトグラフ（ＬＣ／ＭＳ）分析、ガスクロマトグラフ（ＧＣ／ＭＳ）分析、高速原子衝突クロマトグラフ（ＦＡＢ／ＭＳ分析）など）により分子構造を同定し、分子式から求めることができる。 The molecular weight of the polymerizable compound is determined by identifying the molecular structure by mass spectrometry (for example, liquid chromatography (LC / MS) analysis, gas chromatography (GC / MS) analysis, high-speed atom collision chromatography (FAB / MS analysis), etc.). , Can be determined from the molecular formula.
　重合性化合物は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　中でも、重合性化合物を２種以上組み合わせて用いることが、現像時の除去性の点で好ましい。また、現像（好ましくは炭酸現像）する際の残渣の抑制及び膜強度の観点から、２官能の重合性化合物と２官能以外の重合性化合物とを併用することが好ましい。 The polymerizable compound may be used alone or in combination of two or more.
Among them, it is preferable to use a combination of two or more polymerizable compounds from the viewpoint of removability during development. Further, it is preferable to use a bifunctional polymerizable compound and a non-bifunctional polymerizable compound in combination from the viewpoint of suppression of residues during development (preferably carbonic acid development) and film strength.
　遮光層に含まれる重合性化合物の含有量は、組成物の全固形分量に対して、０質量％～５０質量％が好ましく、０質量％～４０質量％がより好ましく、０質量％～３０質量％がさらに好ましい。 The content of the polymerizable compound contained in the light-shielding layer is preferably 0% by mass to 50% by mass, more preferably 0% by mass to 40% by mass, and more preferably 0% by mass to 30% by mass based on the total solid content of the composition. % Is more preferred.
　２官能の重合性化合物と２官能以外の重合性化合物を併用する場合、重合性化合物の全質量（２官能の重合性化合物と２官能以外の重合性化合物との総量）に対する２官能の重合性化合物の質量の比率（２官能の重合性化合物／重合性化合物全質量）が、５０質量％以上であることが好ましい。
　（２官能の重合性化合物／重合性化合物全質量）が５０質量％以上であると、弱アルカリ現像液（例えば、炭酸ナトリウム水溶液）による現像残渣の抑制及び膜強度の点で有利である。 When a bifunctional polymerizable compound and a non-bifunctional polymerizable compound are used in combination, the bifunctional polymerizable with respect to the total mass of the polymerizable compound (the total amount of the bifunctional polymerizable compound and the non-bifunctional polymerizable compound) The mass ratio of the compounds (bifunctional polymerizable compound / total polymerizable compound) is preferably 50% by mass or more.
A content of (bifunctional polymerizable compound / total of polymerizable compound) of 50% by mass or more is advantageous in terms of suppressing a development residue by a weak alkali developing solution (for example, aqueous sodium carbonate solution) and film strength.
～バインダーポリマー及び重合性化合物の量的関係～
　遮光層において、前述のバインダーポリマーの含有量（Ｂ）に対する前述の重合性化合物の含有量（Ｍ）の質量比（Ｍ／Ｂ比）は、０．５０以下であることが好ましい。Ｍ／Ｂ比が０．５０以下であると形成されるパターンの直線性がより良好となる。 -Quantitative relationship between binder polymer and polymerizable compound-
In the light-shielding layer, the mass ratio (M / B ratio) of the content (M) of the polymerizable compound to the content (B) of the binder polymer is preferably 0.50 or less. When the M / B ratio is 0.50 or less, the linearity of the formed pattern becomes better.
－光重合開始剤－
　遮光層は、更に硬化成分として、光重合開始剤の少なくとも一種を含むことができる。
　現像後のパターン形状の良化に効果がある。
　その一方、光重合開始剤を含有しすぎると、例えば他方の側から照射された光が一方の側に達した際にも遮光層の重合反応が進行し、しかもその重合反応は透明基材近傍で進行するため、現像後の遮光層の残渣（現像時の遮光層の除去残り（所謂かぶり）が発生し易くなる場合がある。
　したがって、光重合開始剤の遮光層中における含有量は、光照射領域における遮光層の残渣の悪化を抑える観点から、遮光層の全固形分量に対して、１質量％以下であることが好ましい。上記の理由から、光重合開始剤の含有量は、０．５質量％未満がより好ましく、０質量％（含有しないこと）が更に好ましい。 -Photopolymerization initiator-
The light-shielding layer may further contain at least one photopolymerization initiator as a curing component.
This is effective in improving the pattern shape after development.
On the other hand, if the photopolymerization initiator is contained too much, the polymerization reaction of the light-shielding layer proceeds even when the light irradiated from the other side reaches one side, for example, and the polymerization reaction is close to the transparent substrate. Therefore, residues of the light-shielding layer after development (removal residue of the light-shielding layer during development (so-called fog)) may easily occur.
Therefore, the content of the photopolymerization initiator in the light-shielding layer is preferably 1% by mass or less based on the total solid content of the light-shielding layer, from the viewpoint of suppressing deterioration of the residue of the light-shielding layer in the light irradiation region. For the above-mentioned reasons, the content of the photopolymerization initiator is more preferably less than 0.5% by mass, and further preferably 0% by mass (not contained).
　光重合開始剤としては、特開２０１１－９５７１６号公報の段落００３１～００４２に記載の光重合開始剤、特開２０１５－０１４７８３号公報の段落００６４～００８１に記載のオキシム系光重合開始剤が挙げられる。
　光重合開始剤は、上市されている市販品を使用してもよい。
　市販品としては、例えば、１，２－オクタンジオン－１－［４－（フェニルチオ）－２－（Ｏ－ベンゾイルオキシム）］（商品名：ＩＲＧＡＣＵＲＥ　ＯＸＥ－０１、ＢＡＳＦ社）、１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン－１－（Ｏ－アセチルオキシム）（商品名：ＩＲＧＡＣＵＲＥ　ＯＸＥ－０２、ＢＡＳＦ社製）、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン（商品名：ＩＲＧＡＣＵＲＥ　３７９ＥＧ、ＢＡＳＦ社製）、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン（商品名：ＩＲＧＡＣＵＲＥ　９０７、ＢＡＳＦ社製）、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン（商品名：ＩＲＧＡＣＵＲＥ　１２７、ＢＡＳＦ社製）、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１（商品名：ＩＲＧＡＣＵＲＥ　３６９、ＢＡＳＦ社製）、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン（商品名：ＩＲＧＡＣＵＲＥ　１１７３、ＢＡＳＦ社製）、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン（商品名：ＩＲＧＡＣＵＲＥ　１８４、ＢＡＳＦ社製）、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（商品名：ＩＲＧＡＣＵＲＥ　６５１、ＢＡＳＦ社製）、オキシムエステル系光重合開始剤の商品名：Ｌｕｎａｒ　６（ＤＫＳＨジャパン（株）社製）、２，４－ジエチルチオキサントン（商品名：カヤキュアＤＥＴＸ－Ｓ、日本化薬（株）社製）、フルオレンオキシム系光重合開始剤であるＤＦＩ－０９１、ＤＦＩ－０２０（ともにダイトーケミックス社製）などが好ましく挙げられる。 Examples of the photopolymerization initiator include photopolymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716, and oxime-based photopolymerization initiators described in paragraphs 0064 to 0081 of JP-A-2015-014783. Can be
As the photopolymerization initiator, commercially available products may be used.
Examples of commercially available products include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (trade name: IRGACURE OXE-01, BASF), 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), 2- (dimethylamino)- 2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379EG, manufactured by BASF), 2-methyl-1- (4-methylthio) Phenyl) -2-morpholinopropan-1-one (trade name: IRGACURE 907, manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (trade name: IRGACURE 127, manufactured by BASF), 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1 (trade name: IRGACURE 369, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: IRGACURE 1173, manufactured by BASF) , 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: IRGACURE 184, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: IRGACURE 651, manufactured by BASF), Trade name of oxime ester-based photopolymerization initiator: Lunar 6 (DKSH Japan) Co., Ltd.), 2,4-diethylthioxanthone (trade name: Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.), fluorene oxime-based photopolymerization initiators DFI-091 and DFI-020 (both from Daitomix) And the like.
－界面活性剤－
　遮光層は、界面活性剤の少なくとも一種を含有することができる。
　界面活性剤としては、例えば、特許第４５０２７８４号公報の段落００１７、特開２００９－２３７３６２号公報の段落００６０～００７１に記載の界面活性剤が挙げられる。中でも、遮光層塗布形成時における膜性改良の観点からは、フッ素系界面活性剤（例えば、ＤＩＣ（株）製のメガファック（登録商標）Ｆ－７８４－Ｆ、Ｆ－７８０Ｆ、Ｆ－５５５Ａ等）を用いることが好ましい。 -Surfactant-
The light-shielding layer can contain at least one surfactant.
Examples of the surfactant include the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362. Above all, from the viewpoint of improving the film properties at the time of forming the light-shielding layer, from the viewpoint of improving the film properties, a fluorine-based surfactant (for example, Megafac (registered trademark) F-784-F, F-780F, F-555A, etc., manufactured by DIC Corporation) may be used. ) Is preferably used.
　遮光層が界面活性剤を含有する場合、界面活性剤の遮光層中における含有量としては、遮光層の全質量に対して、０．０１質量％～３質量％が好ましく、０．０５質量％～１質量％がより好ましく、０．１質量％～０．８質量％が更に好ましい。 When the light-shielding layer contains a surfactant, the content of the surfactant in the light-shielding layer is preferably 0.01% by mass to 3% by mass, and more preferably 0.05% by mass, based on the total mass of the light-shielding layer. １1% by mass is more preferable, and 0.1 to 0.8% by mass is further preferable.
－他の成分－
　遮光層は、上記した成分に加え、必要に応じて、重合禁止剤、染料、添加剤等の他の成分を含んでいてもよい。 -Other components-
The light-shielding layer may contain other components such as a polymerization inhibitor, a dye, and an additive, if necessary, in addition to the components described above.
（重合禁止剤）
　遮光層は、重合禁止剤の少なくとも１種を含むことが好ましい。
　遮光層が、重合禁止剤を含むと、現像残渣の発生がより抑制される。重合禁止剤としては、例えば、特許第４５０２７８４号公報の段落００１８に記載の熱重合防止剤（重合禁止剤ともいう。）を用いることができる。中でも、重合禁止剤としては、フェノチアジン、ハイドロキノンモノメチルエーテル等を好適に用いることができる。 (Polymerization inhibitor)
The light-shielding layer preferably contains at least one polymerization inhibitor.
When the light-shielding layer contains a polymerization inhibitor, generation of a development residue is further suppressed. As the polymerization inhibitor, for example, a thermal polymerization inhibitor (also referred to as a polymerization inhibitor) described in paragraph 0018 of Japanese Patent No. 4502784 can be used. Among them, phenothiazine, hydroquinone monomethyl ether, and the like can be suitably used as the polymerization inhibitor.
（染料）
　遮光層は、反射防止能を発現するという観点から染料を含有していてもよい。
　遮光層に含有され得る染料には、特に制限はなく、公知の染料、例えば、「染料便覧」（有機合成化学協会編集、昭和４５年刊）等の文献に記載されている公知の染料、又は、市販品として入手可能な染料を適宜選択して使用することができる。
　染料の具体例としては、アゾ染料、金属錯塩アゾ染料、ピラゾロンアゾ染料、ナフトキノン染料、アントラキノン染料、フタロシアニン染料、カルボニウム染料、キノンイミン染料、メチン染料、シアニン染料、スクアリリウム色素、ピリリウム塩、金属チオレート錯体等の染料が挙げられる。 (dye)
The light-shielding layer may contain a dye from the viewpoint of exhibiting antireflection ability.
There is no particular limitation on the dye that can be contained in the light-shielding layer, and known dyes, for example, known dyes described in documents such as “Dye Handbook” (edited by the Society of Organic Synthetic Chemistry, published in 1970), or A commercially available dye can be appropriately selected and used.
Specific examples of the dye include an azo dye, a metal complex salt azo dye, a pyrazolone azo dye, a naphthoquinone dye, an anthraquinone dye, a phthalocyanine dye, a carbonium dye, a quinone imine dye, a methine dye, a cyanine dye, a squarylium dye, a pyrylium salt, and a metal thiolate complex. Dyes.
　遮光層が染料を含有する場合、染料の含有量は、反射防止能を発現するという観点からは、前述の顔料１００質量部に対して、１質量部～４０質量部であることが好ましく、１質量部～２０質量部であることがより好ましい。染料の含有量が上記範囲であることで、形成された遮光層における反射防止効果、即ち、目視によるぎらつき抑制効果が良好となる。 When the light-shielding layer contains a dye, the content of the dye is preferably 1 part by mass to 40 parts by mass with respect to 100 parts by mass of the above-described pigment from the viewpoint of exhibiting antireflection ability. More preferably, the amount is from 20 parts by mass to 20 parts by mass. When the content of the dye is in the above range, the anti-reflection effect of the formed light-shielding layer, that is, the effect of visually suppressing glare is improved.
（添加剤）
　添加剤としては、特開２０００－３１０７０６号公報の段落００５８～００７１に記載のその他の添加剤が挙げられる。 (Additive)
Examples of the additive include other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.
（不純物）
　遮光層は、不純物の含有量が少ないことが好ましい。
　遮光層における不純物の詳細及び好ましい態様等の詳細については、既述の第１感光層における場合と同様であるので、ここでは記載を省略する。 (impurities)
The light-shielding layer preferably has a low impurity content.
The details of the impurities in the light-shielding layer and the details of preferred embodiments and the like are the same as in the case of the above-described first photosensitive layer, and thus description thereof is omitted here.
　遮光層の厚みは、２０μｍ以下が好ましく、１０μｍ以下がより好ましく、５μｍ以下が特に好ましい。遮光層の厚みが、２０μｍ以下であると、転写フィルム全体の薄膜化の点で有利である。遮光層の厚みは、製造適性の観点から、１μｍ以上が好ましく、２μｍ以上がより好ましい。 厚 み The thickness of the light-shielding layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. When the thickness of the light-shielding layer is 20 μm or less, it is advantageous in terms of making the entire transfer film thinner. The thickness of the light-shielding layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of production suitability.
～遮光層の形成～
　遮光層の形成方法には、特に限定はなく、公知の方法を用いることができる。
　遮光層の形成方法の一例としては、例えば、既述の第１感光層の表面、又は第１感光層上に中間層を有する場合は中間層の表面に、溶剤を含有する遮光層用組成物を塗布等の方法で付与し、必要に応じて乾燥させることによって形成する方法が挙げられる。
　遮光層用組成物は、少なくともバインダーポリマー及び溶剤（特に有機溶剤）、並びに必要に応じて硬化成分、界面活性剤及び添加剤等の他の成分を混合することにより調製することができる。 -Formation of light-shielding layer-
The method for forming the light-shielding layer is not particularly limited, and a known method can be used.
Examples of the method for forming the light-shielding layer include, for example, a composition for a light-shielding layer containing a solvent on the surface of the above-described first photosensitive layer, or on the surface of the intermediate layer when the first photosensitive layer has an intermediate layer. Is applied by a method such as coating and dried if necessary.
The composition for a light-shielding layer can be prepared by mixing at least a binder polymer and a solvent (particularly an organic solvent), and if necessary, other components such as a curing component, a surfactant and an additive.
　塗布の方法及び乾燥の方法については、既述の第１感光層における場合と同様であり、公知の方法を適用することができ、例えば、既述の第１感光層の塗布及び乾燥に用いられる方法と同様の方法が挙げられる。 The method of coating and the method of drying are the same as in the case of the above-described first photosensitive layer, and a known method can be applied. For example, the method is used for coating and drying of the above-described first photosensitive layer. A method similar to the method can be used.
　遮光層に紫外線吸収材料として黒色顔料を用いる場合、黒色顔料は、黒色顔料が分散された分散液として遮光層用組成物に用いられることが望ましい。
　分散液は、黒色顔料と顔料分散剤とを予め混合して得られる混合物を、後述する有機溶剤又はビヒクルに添加して分散させることによって調製することができる。ビヒクルとは、顔料を分散させる媒質部分をいい、液状であって、かつ、黒色顔料と結合して層を形成するバインダー成分とバインダー成分を溶解して希釈する有機溶剤等の媒体とを含む。
　黒色顔料を分散させる際に用いられる分散機としては、特に制限はなく、例えば、「顔料の事典」（第一版、朝倉邦造著、朝倉書店、２０００年、４３８頁）に記載の、ニーダー、ロールミル、アトライター、スーパーミル、ディゾルバ、ホモミキサー、サンドミル等の公知の分散機が挙げられる。さらに、同３１０頁に記載の機械的摩砕によって、分散質である黒色顔料を摩擦力を利用して微粉砕してもよい。
　なお、顔料分散剤は、顔料及び有機溶剤の種類に応じて選択すればよく、例えば市販の分散剤を使用することができる。 When a black pigment is used as the ultraviolet absorbing material in the light-shielding layer, the black pigment is desirably used in the composition for the light-shielding layer as a dispersion in which the black pigment is dispersed.
The dispersion can be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent or a vehicle described below and dispersing the mixture. The vehicle refers to a medium portion in which the pigment is dispersed, and includes a binder component which is liquid and binds to the black pigment to form a layer, and a medium such as an organic solvent which dissolves and dilutes the binder component.
The dispersing machine used for dispersing the black pigment is not particularly limited. For example, a kneader described in “Encyclopedia of Pigments” (1st edition, written by Kunizo Asakura, Asakura Shoten, p. 438, 2000) Known dispersers such as a roll mill, an attritor, a super mill, a dissolver, a homomixer, and a sand mill are exemplified. Further, the black pigment, which is a dispersoid, may be finely pulverized by mechanical grinding described on page 310 using frictional force.
In addition, what is necessary is just to select a pigment dispersing agent according to the kind of a pigment and an organic solvent, For example, a commercially available dispersing agent can be used.
－溶剤－
　遮光層用組成物に用いられる溶剤としては、通常用いられる有機溶剤を特に制限なく用いることができ、例えば、エステル、エーテル、ケトン、芳香族炭化水素等が挙げられる。
　また、溶剤として、米国特許公開２００５／２８２０７３号明細書の段落００５４、００５５に記載のＳｏｌｖｅｎｔと同様に、メチルエチルケトン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート（ＰＥＧＭＥＡ）、シクロヘキサノン、シクロヘキサノール、メチルイソブチルケトン、乳酸エチル、乳酸メチル等を用いることができる。
　中でも、溶剤としては、１－メトキシ－２－プロピルアセテート、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、ジエチレングリコールモノエチルエーテルアセテート（エチルカルビトールアセテート）、ジエチレングリコールモノブチルエーテルアセテート（ブチルカルビトールアセテート）、プロピレングリコールメチルエーテルアセテート、メチルエチルケトン等が好適である。
　溶剤は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　また、溶剤として、必要に応じて、沸点が１８０℃～２５０℃である有機溶剤（高沸点溶剤）を使用することができる。 -solvent-
As the solvent used in the composition for a light-shielding layer, a commonly used organic solvent can be used without any particular limitation, and examples thereof include esters, ethers, ketones, and aromatic hydrocarbons.
Examples of the solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PEGMEA), cyclohexanone, cyclohexanol, and methyl isobutyl as in Solvent described in paragraphs 0054 and 0055 of US Patent Publication 2005/280733. Ketone, ethyl lactate, methyl lactate and the like can be used.
Among them, examples of the solvent include 1-methoxy-2-propyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, Preferred are cyclohexanone, diethylene glycol monoethyl ether acetate (ethyl carbitol acetate), diethylene glycol monobutyl ether acetate (butyl carbitol acetate), propylene glycol methyl ether acetate, methyl ethyl ketone, and the like.
The solvent may be used alone or in combination of two or more.
As a solvent, an organic solvent having a boiling point of 180 ° C. to 250 ° C. (high boiling point solvent) can be used as necessary.
　溶剤を用いる場合、遮光層用組成物の固形分量は、遮光層用組成物の全量に対して、５質量％～８０質量％が好ましく、５質量％～４０質量％がより好ましく、５質量％～３０質量％が特に好ましい。 When a solvent is used, the solid content of the composition for a light-shielding layer is preferably from 5% by mass to 80% by mass, more preferably from 5% by mass to 40% by mass, based on the total amount of the composition for a light-shielding layer. -30% by weight is particularly preferred.
（中間層）
　第１感光層と遮光層との間には、更に、中間層を有する態様が好ましい。
　中間層が第１感光層と遮光層との間に配置されていることにより、塗布後の保存時における、第１感光層中の光重合開始剤の遮光層への移動を抑えることができる。第１感光層から遮光層に光重合開始剤が移動して混合し、遮光層中の光重合開始剤の含有割合が増えると、透明基材の遮光層を有しない側からの光が透明基材を透過して遮光層に入射した際に遮光層での重合反応が進行しやすくなり、またその重合反応は透明基材近傍で進行するため、現像後の遮光層の残渣（現像時の遮光層の除去残り（所謂かぶり）が発生し易くなる。 (Intermediate layer)
An embodiment in which an intermediate layer is further provided between the first photosensitive layer and the light-shielding layer is preferable.
By disposing the intermediate layer between the first photosensitive layer and the light-shielding layer, the movement of the photopolymerization initiator in the first photosensitive layer to the light-shielding layer during storage after coating can be suppressed. When the photopolymerization initiator moves from the first photosensitive layer to the light-shielding layer and mixes, and the content ratio of the photopolymerization initiator in the light-shielding layer increases, light from the side of the transparent substrate that does not have the light-shielding layer becomes transparent. When the light passes through the material and enters the light-shielding layer, the polymerization reaction in the light-shielding layer easily progresses, and the polymerization reaction proceeds near the transparent substrate. Unremoved portions of the layer (so-called fogging) are likely to occur.
　中間層は、バインダーポリマーを含有することが好ましく、水又は炭素数１～４の低級アルコールに対して可溶性を有するバインダーポリマーを含有することがより好ましく、バインダーポリマー及び重合性化合物を含有することが更に好ましい。 The intermediate layer preferably contains a binder polymer, more preferably a binder polymer having solubility in water or a lower alcohol having 1 to 4 carbon atoms, and more preferably contains a binder polymer and a polymerizable compound. More preferred.
－バインダーポリマー－
　中間層は、水又は炭素数１～４の低級アルコールに対して可溶性を有するバインダーポリマーを主成分として含むことが好ましい。このようなバインダーポリマーを含有すると、現像時に除去しやすく、良好なパターンを形成しやすい。 -Binder polymer-
The intermediate layer preferably contains a binder polymer having solubility in water or a lower alcohol having 1 to 4 carbon atoms as a main component. When such a binder polymer is contained, it is easily removed at the time of development, and a good pattern is easily formed.
　本開示において、「主成分として含む」とは、中間層中に含まれるバインダー成分のうち最も多く含有されているバインダーポリマーであるか、又は中間層中に含まれるバインダー成分の全体に占める含有比率が５０質量％以上のバインダーポリマーであることをいう。 In the present disclosure, "contained as a main component" means that the binder polymer contained most in the binder component contained in the intermediate layer, or the content ratio of the binder component contained in the entire intermediate layer Is 50% by mass or more of the binder polymer.
　水又は炭素数１～４の低級アルコールに対して可溶性を有するバインダーポリマーとしては、公知のものの中から適宜選択することができ、例えば、ポリビニルアルコール、ポリビニルピロリドン等が挙げられる。中でも、中間層に用いられるバインダーポリマーとしては、ポリビニルアルコールとポリビニルピロリドンとの組み合わせが好ましい。 The binder polymer having solubility in water or a lower alcohol having 1 to 4 carbon atoms can be appropriately selected from known ones, and examples thereof include polyvinyl alcohol and polyvinyl pyrrolidone. Among them, a combination of polyvinyl alcohol and polyvinylpyrrolidone is preferable as the binder polymer used for the intermediate layer.
　なお、「水又は炭素数１～４の低級アルコールに対して可溶性を有する」とは、２５℃において水又は炭素数１～４の低級アルコール１００ｍｌに対して５ｇ以上溶解する性質をいう。
　ここで、水としては、イオン交換水、蒸留水等が挙げられる。
　また、炭素数１～４の低級アルコールとしては、例えば、メタノール、エタノール、プロパノール、イソプロパノール、及びブタノールが挙げられる。 Here, “has solubility in water or a lower alcohol having 1 to 4 carbon atoms” means that 5 g or more is dissolved in 100 ml of water or a lower alcohol having 1 to 4 carbon atoms at 25 ° C.
Here, examples of the water include ion-exchanged water and distilled water.
The lower alcohol having 1 to 4 carbon atoms includes, for example, methanol, ethanol, propanol, isopropanol and butanol.
　中間層に含まれるバインダーポリマーの含有量は、中間層の全固形分量に対して、８０質量％以上が好ましく、９０質量％以上がより好ましい。上限値は、特に制限はなく、１００質量％以下の範囲で調整すればよい。 含有 The content of the binder polymer contained in the intermediate layer is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total solid content of the intermediate layer. The upper limit is not particularly limited, and may be adjusted within a range of 100% by mass or less.
－重合性化合物－
　中間層は、更に、重合性化合物の少なくとも一種を含むことが好ましい。
　重合性化合物を含有することは、現像（好ましくは炭酸現像）する際の残渣の抑制の点で好ましい。 -Polymerizable compound-
The intermediate layer preferably further contains at least one polymerizable compound.
It is preferable to contain a polymerizable compound from the viewpoint of suppressing residues during development (preferably, carbon dioxide development).
　中間層に用いることができる重合性化合物としては、第１感光層又は遮光層に用いることができる重合性化合物と同様のものを適宜選択して用いることができ、重合性モノマーが好ましい。中でも、水への溶解性の観点から、アクリルアミドモノマー（例えば、富士フイルム（株）製のＦＡＭ－４０１、ＦＡＭ－３０１、ＦＡＭ－２０１、ＦＡＭ－４０２等）が好ましい。
　重合性化合物は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　中間層に含まれる重合性化合物の含有量は、中間層の全固形分量に対して、５０質量％以下が好ましく、３０質量％以下がより好ましい。 As the polymerizable compound that can be used for the intermediate layer, the same compound as the polymerizable compound that can be used for the first photosensitive layer or the light-shielding layer can be appropriately selected and used, and a polymerizable monomer is preferable. Among them, acrylamide monomers (for example, FAM-401, FAM-301, FAM-201, FAM-402, etc., manufactured by Fuji Film Co., Ltd.) are preferable from the viewpoint of solubility in water.
The polymerizable compound may be used alone or in combination of two or more.
The content of the polymerizable compound contained in the intermediate layer is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total solid content of the intermediate layer.
－光重合開始剤－
　中間層は、更に、光重合開始剤の少なくとも一種を含んでもよい。
　中間層に用いることができる光重合開始剤としては、例えば、第１感光層又は遮光層に用いることができる光重合開始剤と同様のものを適宜選択して用いることができる。
　中間層が光重合開始剤を含有すると、現像後のパターン形状の良化に効果がある。
　中間層に含まれる光重合開始剤の含有量は、中間層の全固形分量に対して、１０質量％以下が好ましく、５質量％以下がより好ましい。 -Photopolymerization initiator-
The intermediate layer may further include at least one photopolymerization initiator.
As the photopolymerization initiator that can be used for the intermediate layer, for example, the same photopolymerization initiator that can be used for the first photosensitive layer or the light-shielding layer can be appropriately selected and used.
When the intermediate layer contains a photopolymerization initiator, it is effective in improving the pattern shape after development.
The content of the photopolymerization initiator contained in the intermediate layer is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total solid content of the intermediate layer.
－界面活性剤－
　中間層は、界面活性剤の少なくとも一種を含有することができる。
　界面活性剤としては、中間層を塗布形成する際の膜性改良の観点から、フッ素含有界面活性剤（例えば、ＤＩＣ（株）製のメガファック（登録商標）Ｆ－７８４Ｆ、Ｆ－７８０Ｆ、Ｆ－４４４等）などを挙げることができる。
　中間層に含まれる界面活性剤の含有量は、中間層の全固形分量に対して、０．００１質量％～１質量％が好ましく、０．００１質量％～０．５質量％がより好ましく、０．００１質量％～０．１質量％がさらに好ましい。 -Surfactant-
The intermediate layer can contain at least one surfactant.
As the surfactant, a fluorine-containing surfactant (eg, Megafac (registered trademark) F-784F, F-780F, F-780F, F-780F, -444 etc.).
The content of the surfactant contained in the intermediate layer is preferably from 0.001% by mass to 1% by mass, more preferably from 0.001% by mass to 0.5% by mass, based on the total solid content of the intermediate layer, 0.001% by mass to 0.1% by mass is more preferred.
－他の成分－
　中間層は、必要に応じて、添加剤等の他の成分を含んでいてもよい。添加剤については、遮光層に添加できる添加剤と同様である。 -Other components-
The intermediate layer may include other components such as additives as necessary. The additives are the same as the additives that can be added to the light shielding layer.
　中間層の厚みは、０．２μｍ～５μｍが好ましく、０．５μｍ～３μｍがより好ましく、０．８μｍ～２μｍが更に好ましい。 The thickness of the intermediate layer is preferably 0.2 μm to 5 μm, more preferably 0.5 μm to 3 μm, and still more preferably 0.8 μm to 2 μm.
～中間層の形成～
　中間層の形成方法には、特に限定はなく、公知の方法を用いることができる。
　中間層の形成方法としては、例えば既述の第１感光層の表面に溶剤を含有する中間層用組成物を塗布等の方法で付与し、必要に応じて乾燥させることによって形成する方法が挙げられる。
　中間層用組成物は、少なくともバインダーポリマー及び水性溶媒、並びに必要に応じて硬化成分、界面活性剤及び添加剤等の他の成分を混合して調製することができる。中間層用組成物の調製には、第１感光層及び遮光層とは異なる溶剤を用いることが好ましく、水性溶媒が好適に用いられる。水性溶媒としては、水、水と水に可能性の有機溶剤との混合溶媒等が挙げられる。中間層用組成物は、水系組成物であることが好ましい。 ~ Formation of intermediate layer ~
The method for forming the intermediate layer is not particularly limited, and a known method can be used.
Examples of the method for forming the intermediate layer include a method in which the intermediate layer composition containing a solvent is applied to the surface of the above-described first photosensitive layer by a method such as coating, and dried if necessary. Can be
The composition for an intermediate layer can be prepared by mixing at least a binder polymer and an aqueous solvent, and if necessary, other components such as a curing component, a surfactant and an additive. In preparing the composition for the intermediate layer, it is preferable to use a solvent different from the first photosensitive layer and the light-shielding layer, and an aqueous solvent is suitably used. Examples of the aqueous solvent include water, and a mixed solvent of water and an organic solvent capable of being water. The composition for the intermediate layer is preferably an aqueous composition.
　塗布の方法及び乾燥の方法については、既述の第１感光層における場合と同様であり、公知の方法を適用することができ、例えば、既述の第１感光層の塗布及び乾燥に用いられる方法と同様の方法が挙げられる。 The method of coating and the method of drying are the same as in the case of the above-described first photosensitive layer, and a known method can be applied. For example, the method is used for coating and drying of the above-described first photosensitive layer. A method similar to the method can be used.
（保護フィルム）
　本開示の転写フィルムには、仮支持体の上に積層された遮光層の表面に保護フィルムを有することができる。保護フィルムが付設されることで、保管の際の異物等の不純物による汚染及び露出面の損傷から保護することができる。 (Protective film)
The transfer film of the present disclosure may have a protective film on the surface of the light-shielding layer laminated on the temporary support. By providing the protective film, it is possible to protect from contamination by impurities such as foreign matter and damage to the exposed surface during storage.
　保護フィルムには、遮光層から容易に剥離し得るものが好ましく、後述する仮支持体と同一又は類似の基材を用いることができる。
　保護フィルムの例としては、ポリオレフィンフィルム（例えば、ポリプロピレン（ＰＰ）フィルム、ポリエチレン（ＰＥ）フィルム等）、ポリエチレンテレフタレート（ＰＥＴ）フィルム、シリコン紙、又はポリテトラフルオロエチレンフィルムなどが挙げられる。
　また、特開２００６－２５９１３８号公報の段落００８３～００８７及び００９３に記載の保護フィルムを適宜使用することができる。 The protective film is preferably one that can be easily peeled off from the light-shielding layer, and the same or similar base material as the temporary support described later can be used.
Examples of the protective film include a polyolefin film (for example, a polypropylene (PP) film, a polyethylene (PE) film or the like), a polyethylene terephthalate (PET) film, silicon paper, a polytetrafluoroethylene film, or the like.
Further, the protective films described in paragraphs 0083 to 0087 and 0093 of JP-A-2006-259138 can be appropriately used.
　保護フィルムの厚みは、０．２μｍ～４０μｍが好ましく、０．５μｍ～３０μｍがより好ましい。 (4) The thickness of the protective film is preferably from 0.2 μm to 40 μm, more preferably from 0.5 μm to 30 μm.
（仮支持体）
　仮支持体は、転写フィルムからの剥離の点で、樹脂製の基材が好ましく、成形後に可撓性を呈する材料を用いた基材がより好ましい。基材としては、フィルム又はシートのいずれでもよい。
　また、仮支持体は、透明性を有するものでもよいし、着色（例えば、染料化ケイ素、アルミナゾル、クロム塩、ジルコニウム塩等を含有して着色）されたものでもよい。 (Temporary support)
The temporary support is preferably a resin substrate in terms of peeling from the transfer film, and more preferably a substrate using a material exhibiting flexibility after molding. The substrate may be either a film or a sheet.
The temporary support may have transparency or may be colored (for example, colored by containing dyed silicon, alumina sol, chromium salt, zirconium salt, etc.).
　仮支持体の例としては、シクロオレフィンコポリマー基材、ポリエチレンテレフタレート（ＰＥＴ）基材、トリ酢酸セルロース基材、ポリスチレン基材、ポリカーボネート基材等が挙げられ、中でも、ハンドリングの観点から、ＰＥＴ基材が特に好ましい。 Examples of the temporary support include a cycloolefin copolymer substrate, a polyethylene terephthalate (PET) substrate, a cellulose triacetate substrate, a polystyrene substrate, and a polycarbonate substrate. Among them, from the viewpoint of handling, a PET substrate Is particularly preferred.
　仮支持体としては、導電性が付与された仮支持体も好適であり、導電性は、例えば特開２００５－２２１７２６号公報に記載の方法等により付与されてもよい。 (4) As the temporary support, a temporary support having conductivity is also suitable, and the conductivity may be provided by, for example, the method described in JP-A-2005-221726.
　仮支持体の厚みとしては、５μｍ～６０μｍが好ましく、５μｍ～４０μｍがより好ましい。 (4) The thickness of the temporary support is preferably 5 μm to 60 μm, more preferably 5 μm to 40 μm.
　本開示の転写フィルムの一例を図１を参照して説明する。
　本開示の転写フィルムは、仮支持体上に第１感光層と遮光層とを少なくとも有し、第１感光層と遮光層との間に中間層を有してもよい。
　転写フィルム１０は、図１に示すように、仮支持体１９の上に、仮支持体側から順に第１感光層１７、中間層１５、遮光層１３、及び保護フィルム１１が積層された積層構造を有している。中間層１５が第１感光層１７と遮光層１３との間に設けられることにより、第１感光層１７から遮光層１３への光重合開始剤の移動が抑えられる。これにより、積層体を作製して例えば透明基材の両側より光照射された際の遮光層中での重合反応が抑えられ、現像残渣の発生が抑制される。また、保護フィルム１１は、後述のように積層体を作製する際に剥離除去される。
　なお、転写フィルムは、図１に示す積層構造に限られるものではなく、図２の積層体に示されるように、中間層を有しない積層構造でもよい。 An example of the transfer film of the present disclosure will be described with reference to FIG.
The transfer film of the present disclosure may include at least a first photosensitive layer and a light shielding layer on a temporary support, and may have an intermediate layer between the first photosensitive layer and the light shielding layer.
As shown in FIG. 1, the transfer film 10 has a laminated structure in which a first photosensitive layer 17, an intermediate layer 15, a light shielding layer 13, and a protective film 11 are laminated on a temporary support 19 in this order from the temporary support. Have. By providing the intermediate layer 15 between the first photosensitive layer 17 and the light-shielding layer 13, the movement of the photopolymerization initiator from the first photosensitive layer 17 to the light-shielding layer 13 is suppressed. This suppresses the polymerization reaction in the light-shielding layer when the laminate is manufactured and irradiated with light from both sides of the transparent substrate, for example, and the generation of development residues is suppressed. Further, the protective film 11 is peeled and removed at the time of producing a laminate as described later.
The transfer film is not limited to the laminated structure shown in FIG. 1, but may be a laminated structure having no intermediate layer as shown in the laminated body in FIG.
　本開示の一実施形態である転写フィルムは、例えば、タッチパネル等の画像表示装置に配される金属配線基板の配線パターンを形成するための転写フィルムとして用いることができる。
　本開示の転写フィルムを用いて透明基材に第１感光層、遮光層等を転写し、パターンを形成する方法については後述する。 The transfer film according to an embodiment of the present disclosure can be used, for example, as a transfer film for forming a wiring pattern of a metal wiring substrate provided in an image display device such as a touch panel.
A method of transferring a first photosensitive layer, a light-shielding layer, and the like to a transparent substrate using the transfer film of the present disclosure to form a pattern will be described later.
　転写フィルムは、公知の方法で保管することができる。
　保管の際、雰囲気を大気とすることも可能であり、窒素とすることも可能である。
　保管温度は、公知の温度とすることができ、例えば、室温（２０℃～２５℃）、冷蔵温度（０℃～５℃）、冷凍温度（－５０℃～－１０℃）を挙げることができる。保管温度は、転写フィルムの予期せぬ劣化を防ぐという観点から、冷凍温度又は冷蔵温度が好ましい。具体的には、保管温度は、５℃、－１０℃、－２０℃、－３０℃を挙げることができる。
　また、保管期間に特に制限はなく、例えば、転写フィルムを製造後、５℃で２０日間保管した後に使用する態様、－２０℃で５０日間保管した後に使用する態様などを挙げることができる。  The transfer film can be stored by a known method.
At the time of storage, the atmosphere can be air or nitrogen.
The storage temperature can be a known temperature, for example, room temperature (20 ° C. to 25 ° C.), refrigeration temperature (0 ° C. to 5 ° C.), and freezing temperature (−50 ° C. to −10 ° C.). . The storage temperature is preferably a freezing temperature or a refrigeration temperature from the viewpoint of preventing unexpected deterioration of the transfer film. Specifically, the storage temperature includes 5 ° C., −10 ° C., −20 ° C., and −30 ° C.
The storage period is not particularly limited, and examples thereof include an embodiment in which the transfer film is manufactured and stored at 5 ° C. for 20 days after use, and an embodiment in which the transfer film is stored at −20 ° C. for 50 days.
＜積層体＞
　本開示の積層体は、透明基材と、透明基材の上に積層された既述の本開示の転写フィルムと、を有し、必要に応じて、更に他の層を有するものでもよい。 <Laminate>
The laminate of the present disclosure includes a transparent substrate and the above-described transfer film of the present disclosure laminated on the transparent substrate, and may further include another layer as necessary.
　本開示の転写フィルムの詳細については、既述の通りであり、転写フィルムを構成する仮支持体、第１感光層、遮光層、及び中間層の詳細並びに好ましい態様については、既述の通りである。 The details of the transfer film of the present disclosure are as described above, and the details and preferred embodiments of the temporary support, the first photosensitive layer, the light-shielding layer, and the intermediate layer that constitute the transfer film are as described above. is there.
（透明基材）
　透明基材は、透明性を有する基材のことであり、光学的に歪みがなく、透明度が高い材料であることが好ましい。なお、本開示における透明とは、全可視光線の透過率が８５％以上であることを意図し、９０％以上が好ましく、９５％以上がより好ましい。 (Transparent substrate)
The transparent substrate is a substrate having transparency, and is preferably a material having no optical distortion and high transparency. The term “transparent” in the present disclosure means that the transmittance of all visible light is 85% or more, and is preferably 90% or more, and more preferably 95% or more.
　本開示における透明基材としては、ガラス基材、又は樹脂基材が好ましい。
　中でも、軽量であり、破損しにくい点で、樹脂基材が好ましい。樹脂基材の例としては、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート、ポリカーボネート（ＰＣ）、トリアセチルセルロース（ＴＡＣ）、シクロオレフィンポリマー（ＣＯＰ）等の樹脂からなる透明基材が挙げられる。 As the transparent substrate in the present disclosure, a glass substrate or a resin substrate is preferable.
Above all, a resin base material is preferable because it is lightweight and hard to break. Examples of the resin substrate include a transparent substrate made of a resin such as polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate (PC), triacetyl cellulose (TAC), and cycloolefin polymer (COP).
　透明基材は、表示画像の視認性をより改善する観点から、屈折率が１．６～１．７８であり、かつ、厚みが５０μｍ～２００μｍであることが好ましい。 From the viewpoint of further improving the visibility of the displayed image, the transparent substrate preferably has a refractive index of 1.6 to 1.78 and a thickness of 50 μm to 200 μm.
　透明基材は、単層構造であってもよく、２層以上の積層構造であってもよい。
　透明基材が２層以上の積層構造である場合、屈折率は、透明基材全層での屈折率を意味する。
　透明基材の厚みは、透明基材が２層以上の積層構造を有する場合、全層での合計厚みを意味する。 The transparent substrate may have a single-layer structure or a laminate structure of two or more layers.
When the transparent substrate has a laminated structure of two or more layers, the refractive index means the refractive index of all layers of the transparent substrate.
When the transparent base material has a laminated structure of two or more layers, the thickness of the transparent base material means the total thickness of all the layers.
　透明基材としては、少なくとも一方の面に導電性の部材（例えば、電極、配線）を有する基材が好ましく、両方の面に電極及び配線の少なくとも一方を有する基材がより好ましい。
　本開示においては、透明基材が、タッチパネル用電極及びタッチパネル用配線の少なくとも一方を有する基材であることが好ましい。 As the transparent substrate, a substrate having a conductive member (for example, an electrode or a wiring) on at least one surface is preferable, and a substrate having at least one of an electrode and a wiring on both surfaces is more preferable.
In the present disclosure, the transparent substrate is preferably a substrate having at least one of a touch panel electrode and a touch panel wiring.
　導電性の部材に用いられる導電性材料としては、透明導電材料及び金属材料が好ましい。透明導電材料としては、例えば、ＩＴＯ（酸化インジウムスズ）、ＩＺＯ（酸化インジウム亜鉛）等の金属酸化膜が好ましい。金属材料としては、金、銀、銅、モリブデン、アルミニウム、チタン、クロム、亜鉛及びマンガン、並びに、これらの金属元素の２種以上からなる合金が挙げられる。 透明 As the conductive material used for the conductive member, a transparent conductive material and a metal material are preferable. As the transparent conductive material, for example, a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide) is preferable. Examples of the metal material include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements.
　タッチパネル用途の場合、タッチパネル用電極として、例えば、タッチパネルの少なくとも画像表示領域に配置される透明電極パターンが挙げられる。タッチパネル用電極は、画像表示領域からタッチパネルの枠部にまで延びていてもよい。
　また、タッチパネル用配線として、例えば、タッチパネルの枠部に配置される引き回し配線（取り出し配線）が挙げられ、金属材料が好適である。引き回し配線の材質としては、銅、モリブデン、アルミニウム又はチタンが好ましく、銅が特に好ましい。 In the case of a touch panel application, examples of the touch panel electrode include a transparent electrode pattern disposed at least in an image display area of the touch panel. The touch panel electrode may extend from the image display area to the frame of the touch panel.
Further, as the wiring for the touch panel, for example, a drawing wiring (extraction wiring) arranged in a frame portion of the touch panel is cited, and a metal material is preferable. As a material of the routing wiring, copper, molybdenum, aluminum or titanium is preferable, and copper is particularly preferable.
（第２感光層）
　本開示の積層体は、透明基材の一方の側に既述の第１感光層を有し、かつ、透明基材の他方の側（即ち、透明基材の本開示の転写フィルムが積層された側と反対側）に、更に、第２感光層を有することが好ましい。
　本開示の積層体が第２感光層を有する場合、透明基材の両方の側にそれぞれレジストパターン（好ましくは、互いにパターンの異なるレジストパターン）を付設することができ、透明基材の両側に精細な配線パターン（好ましくは、互いにパターンの異なる配線パターン）を形成することができる。 (Second photosensitive layer)
The laminate of the present disclosure has the above-described first photosensitive layer on one side of the transparent substrate, and the other side of the transparent substrate (that is, the transfer film of the present disclosure of the transparent substrate is laminated thereon). It is preferable to further include a second photosensitive layer on the side opposite to the opposite side).
When the laminate of the present disclosure has the second photosensitive layer, a resist pattern (preferably a resist pattern having a different pattern from each other) can be provided on each side of the transparent substrate, and fine patterns can be formed on both sides of the transparent substrate. Wiring patterns (preferably, wiring patterns having different patterns from each other) can be formed.
　第２感光層は、既述の第１感光層と同一の層でもよいし、相互に異なる層であってもよい。第２感光層は、成分組成が第１感光層と同一の層である場合が好ましい。
　この場合、透明基材の一方の側に第１感光層を設け、他方の側に第２感光層が設けられ、同一の光源を用いて同時に光照射することが可能である。第１感光層と第２感光層とは、異なる光源を用いて照射してもよく、照射する光の波長も異なっていてもよい。 The second photosensitive layer may be the same layer as the above-described first photosensitive layer, or may be different layers. The second photosensitive layer is preferably a layer having the same component composition as the first photosensitive layer.
In this case, a first photosensitive layer is provided on one side of the transparent substrate, and a second photosensitive layer is provided on the other side, and it is possible to simultaneously irradiate light using the same light source. The first photosensitive layer and the second photosensitive layer may be irradiated using different light sources, and the wavelengths of the irradiated light may be different.
　第２感光層は、少なくともバインダーポリマー、重合性化合物、及び光重合開始剤を含む層とすることができ、必要に応じて、更に、界面活性剤、溶剤、添加剤等の他の成分を含んでもよい。
　第２感光層におけるバインダーポリマー、重合性化合物、光重合開始剤、界面活性剤、溶剤、添加剤等の他の成分の詳細及び好ましい態様については、第１感光層における場合と同様である。
　第２感光層は、バインダーポリマー、重合性化合物、及び光重合開始剤を含有することが好ましい。 The second photosensitive layer can be a layer containing at least a binder polymer, a polymerizable compound, and a photopolymerization initiator, and further contains other components such as a surfactant, a solvent, and an additive, if necessary. May be.
Details and preferred embodiments of other components such as a binder polymer, a polymerizable compound, a photopolymerization initiator, a surfactant, a solvent, and an additive in the second photosensitive layer are the same as those in the first photosensitive layer.
The second photosensitive layer preferably contains a binder polymer, a polymerizable compound, and a photopolymerization initiator.
　第２感光層の厚みは、２０μｍ以下が好ましく、１５μｍ以下がより好ましく、１２μｍ以下が特に好ましい。第２感光層の厚みが２０μｍ以下であると、転写フィルム全体の薄膜化、第２感光層又は得られる硬化膜の透過率向上、及び第２感光層又は得られる硬化膜の黄着色化抑制等の点で有利である。
　第２感光層の厚みは、製造適性の観点から、１μｍ以上が好ましく、２μｍ以上がより好ましく、３μｍ以上が特に好ましい。 The thickness of the second photosensitive layer is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 12 μm or less. When the thickness of the second photosensitive layer is 20 μm or less, the entire transfer film is made thinner, the transmittance of the second photosensitive layer or the obtained cured film is improved, and yellowing of the second photosensitive layer or the obtained cured film is suppressed. It is advantageous in the point.
The thickness of the second photosensitive layer is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably 3 μm or more from the viewpoint of production suitability.
～第２感光層の形成～
　第２感光層の形成方法は特に限定されず、公知の方法を用いることができる。
　第２感光層は、例えば、透明基材の上に、第２感光層形成用の塗布液（第２感光層用塗布液）を塗布する方法、又は透明基材の上に、既述の本開示の転写フィルムとは異なる転写材料を貼り合わせる方法により形成することができる。
　後者では、転写材料として、例えば、仮支持体と仮支持体上に第２感光層用塗布液を塗布し乾燥することで形成された第２感光層とを有する転写フィルムを用いることができ、仮支持体と第２感光層との間に更に他の層（例えば既述の中間層）を有する転写フィルムを用いてもよい。
　なお、第２感光層用塗布液を塗布、乾燥する方法は、既述の第１感光層における場合と同様であり、公知の方法を適用することができ、例えば、既述の第１感光層の塗布及び乾燥に用いられる方法と同様の方法が挙げられる。 ~ Formation of the second photosensitive layer ~
The method for forming the second photosensitive layer is not particularly limited, and a known method can be used.
The second photosensitive layer is formed, for example, by applying a coating solution for forming the second photosensitive layer (coating solution for the second photosensitive layer) on a transparent substrate, or by applying the above-described book on the transparent substrate. It can be formed by a method of attaching a transfer material different from the disclosed transfer film.
In the latter, as the transfer material, for example, a transfer film having a temporary support and a second photosensitive layer formed by applying and drying a coating solution for the second photosensitive layer on the temporary support can be used, A transfer film having another layer (for example, the above-described intermediate layer) between the temporary support and the second photosensitive layer may be used.
The method of applying and drying the coating solution for the second photosensitive layer is the same as in the case of the first photosensitive layer described above, and a known method can be applied. And the same method as the method used for coating and drying.
＜パターン形成方法＞
　本開示のパターン形成方法は、透明基材の一方の側に、既述の本開示の転写フィルムを貼り合わせる工程（以下、貼り合わせ工程）と、透明基材の他方の側に、バインダーポリマー、重合性化合物、及び光重合開始剤を含む第２感光層を形成する工程（以下、第２感光層形成工程）と、透明基材の両方の側に対して、光をそれぞれ異なるパターンにて照射する工程（以下、光照射工程）と、照射が行われた後の透明基材の両方の側を現像処理することで、透明基材の両方の側にそれぞれ異なるパターンを形成する工程（以下、パターン化工程）と、を有している。
　また、本開示のパターン形成方法は、必要に応じて、更に、他の工程を有するものであってもよい。 <Pattern forming method>
The pattern forming method of the present disclosure includes a step of laminating the above-described transfer film of the present disclosure on one side of a transparent substrate (hereinafter, a laminating step), and a binder polymer on the other side of the transparent substrate. A step of forming a second photosensitive layer containing a polymerizable compound and a photopolymerization initiator (hereinafter, a second photosensitive layer forming step), and irradiating light to both sides of the transparent substrate in different patterns. (Hereinafter, light irradiation step) and a step of forming different patterns on both sides of the transparent substrate by developing both sides of the transparent substrate after the irradiation is performed (hereinafter, referred to as Patterning step).
Further, the pattern forming method of the present disclosure may further include another step as necessary.
（貼り合わせ工程）
　貼り合わせ工程では、透明基材の一方の側に、既述の本開示の転写フィルムを貼り合わせる。
　本工程では、本開示の転写フィルムを透明基材の一方の側（例えば、電極等が配置された側）に例えばラミネートする等の方法で貼り合わせることができる。
　ラミネートは、真空ラミネーター、オートカットラミネーター等の公知のラミネーターを用いて行うことができる。 (Lamination process)
In the bonding step, the above-described transfer film of the present disclosure is bonded to one side of the transparent substrate.
In this step, the transfer film of the present disclosure can be attached to one side of the transparent substrate (for example, the side on which the electrodes and the like are arranged) by, for example, laminating.
Lamination can be performed using a known laminator such as a vacuum laminator and an auto-cut laminator.
　ラミネート条件としては、一般的な条件を適用できる。
　ラミネート温度としては、８０℃～１５０℃が好ましく、９０℃～１５０℃がより好ましく、１００℃～１５０℃が特に好ましい。ラミネート温度は、ロールを備えたラミネーターのロールの表面温度（以下、ロール温度）を指す。
　ラミネート時の透明基材の温度には、特に制限はない。ラミネート時の透明基材の温度としては、１０℃～１５０℃が好ましく、２０℃～１５０℃がより好ましく、３０℃～１５０℃が更に好ましい。
　また、ラミネート時の線圧としては、０．５ＭＰａ～１０ＭＰａが好ましく、０．５ＭＰａ～５ＭＰａがより好ましく、０．５ＭＰａ～１ＭＰａが特に好ましい。
　また、ラミネート時の搬送速度（ラミネート速度）としては、０．５ｍ／分～５ｍ／分が好ましく、１．５ｍ／分～３ｍ／分がより好ましい。 General conditions can be applied as laminating conditions.
The lamination temperature is preferably from 80 ° C to 150 ° C, more preferably from 90 ° C to 150 ° C, and particularly preferably from 100 ° C to 150 ° C. The lamination temperature refers to a surface temperature of a roll of a laminator provided with the roll (hereinafter, roll temperature).
The temperature of the transparent substrate during lamination is not particularly limited. The temperature of the transparent substrate during lamination is preferably from 10 ° C to 150 ° C, more preferably from 20 ° C to 150 ° C, even more preferably from 30 ° C to 150 ° C.
The linear pressure during lamination is preferably 0.5 MPa to 10 MPa, more preferably 0.5 MPa to 5 MPa, and particularly preferably 0.5 MPa to 1 MPa.
Further, the transport speed (lamination speed) during lamination is preferably from 0.5 m / min to 5 m / min, more preferably from 1.5 m / min to 3 m / min.
　保護フィルム／遮光層／中間層／第１感光層／仮支持体の積層構造を有する転写フィルムを用いる場合には、まず、転写フィルムから保護フィルムを剥離して遮光層を露出させる。次いで、露出した遮光層と、透明基材の電極等が配置された側の面とが接するようにして、転写フィルムと透明基材とを貼り合わせる。
　これにより、転写フィルムの遮光層が透明基材と密着され、仮支持体／第１感光層／中間層／遮光層／電極等／透明基材の積層構造を有する積層体が形成される。
　この積層構造のうち、電極等は透明基材の一部であり、例えばタッチパネル用基板として用いられる。
　その後、必要に応じ、上記積層体から仮支持体を剥離する。 When using a transfer film having a laminated structure of protective film / light-shielding layer / intermediate layer / first photosensitive layer / temporary support, first, the protective film is peeled off from the transfer film to expose the light-shielding layer. Next, the transfer film and the transparent substrate are bonded together such that the exposed light-shielding layer is in contact with the surface of the transparent substrate on which the electrodes and the like are arranged.
Thereby, the light-shielding layer of the transfer film is brought into close contact with the transparent substrate, and a laminate having a laminated structure of temporary support / first photosensitive layer / intermediate layer / light-shielding layer / electrode / transparent substrate is formed.
In this laminated structure, the electrodes and the like are a part of the transparent substrate, and are used, for example, as a substrate for a touch panel.
Thereafter, if necessary, the temporary support is peeled from the laminate.
（第２感光層形成工程）
　第２感光層形成工程では、透明基材の他方の側、即ち第１感光層及び遮光層を有しない側に、バインダーポリマー、重合性化合物、及び光重合開始剤を含む第２感光層を形成する。
　第２感光層の形成は、既述のように、例えば、透明基材の上に、第２感光層形成用の塗布液（第２感光層用塗布液）を塗布する方法、又は透明基材の上に、既述の本開示の転写フィルムとは異なる転写材料を貼り合わせる方法のいずれの方法により形成してもよい。 (Second photosensitive layer forming step)
In the second photosensitive layer forming step, a second photosensitive layer containing a binder polymer, a polymerizable compound, and a photopolymerization initiator is formed on the other side of the transparent substrate, that is, on a side having no first photosensitive layer and no light-shielding layer. I do.
As described above, the formation of the second photosensitive layer is performed, for example, by applying a coating solution for forming the second photosensitive layer (a coating solution for the second photosensitive layer) on a transparent base material, or by using a transparent base material. The transfer film may be formed by any of the above-described methods of attaching a transfer material different from the transfer film of the present disclosure.
　第２感光層用塗布液を塗布、乾燥する方法については、既述の第１感光層の形成における場合と同様に、公知の方法を適用でき、例えば、既述の第１感光層の塗布及び乾燥に用いられる方法と同様の方法が挙げられる。
　転写材料を貼り合わせる方法については、既述の貼り合わせ工程と同様に行うことができる。 As for the method of applying and drying the coating solution for the second photosensitive layer, a known method can be applied in the same manner as in the formation of the first photosensitive layer described above. The same method as the method used for drying may be mentioned.
The method of bonding the transfer material can be performed in the same manner as in the bonding step described above.
（光照射工程）
　光照射工程では、透明基材の両方の側に対して、光をそれぞれ異なるパターンにて照射する。つまり、本工程では、露光部と非露光部とが存在する態様のパターン露光を行う。
　本工程において、透明基材に対して第１感光層が配置されている側から照射された光によって、第１感光層のうちパターン露光された露光部が硬化され、最終的に硬化膜となる。また、第２感光層においても、透明基材に対して第２感光層が配置されている側から照射された光によって、第２感光層のうちパターン露光された露光部が硬化され、最終的に硬化膜となる。
　一方、第１感光層及び第２感光層のうち、パターン露光における非露光部は硬化せず、次のパターン化工程で、現像液によって除去（溶解）される。非露光部は、現像工程後、硬化膜の開口部を形成し得る。
　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。 (Light irradiation step)
In the light irradiation step, light is irradiated on both sides of the transparent substrate in different patterns. That is, in this step, pattern exposure is performed in such a manner that there is an exposed portion and a non-exposed portion.
In this step, the light irradiated from the side on which the first photosensitive layer is disposed with respect to the transparent base material cures the exposed portion of the first photosensitive layer that has been subjected to pattern exposure, and finally becomes a cured film . Also, in the second photosensitive layer, the pattern-exposed exposed portion of the second photosensitive layer is cured by the light irradiated from the side on which the second photosensitive layer is disposed with respect to the transparent base material, and finally, Becomes a cured film.
On the other hand, of the first photosensitive layer and the second photosensitive layer, the non-exposed portions in the pattern exposure are not cured, and are removed (dissolved) by a developer in the next patterning step. The non-exposed portion may form an opening of the cured film after the developing step.
The pattern exposure may be exposure through a mask or digital exposure using a laser or the like.
　パターン露光の光源としては、感光性層を硬化し得る波長域の光（例えば、３６５ｎｍ又は４０５ｎｍ）を照射できるものであれば適宜選定して用いることができる。
　光源としては、例えば、各種レーザー、発光ダイオード（ＬＥＤ）、超高圧水銀灯、高圧水銀灯、及び、メタルハライドランプが挙げられる。露光量は、好ましくは５ｍＪ／ｃｍ２～２００ｍＪ／ｃｍ２であり、より好ましくは１０ｍＪ／ｃｍ２～２００ｍＪ／ｃｍ２である。 As a light source for pattern exposure, any light source that can irradiate light (for example, 365 nm or 405 nm) in a wavelength range that can cure the photosensitive layer can be appropriately selected and used.
Examples of the light source include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. Exposure is preferably 5mJ / cm 2 ~ 200mJ / cm 2, more preferably 10mJ / cm 2 ~ 200mJ / cm 2.
　転写フィルムを用いて透明基板上に第１感光層及び第２感光層を形成した場合、仮支持体を剥離する前にパターン露光し、その後に仮支持体を剥離してもよいし、仮支持体を剥離してからパターン露光してもよい。
　また、本工程では、パターン露光後であってパターン化工程前（即ち、現像前）に、第１感光層及び第２感光層に対して熱処理（いわゆるＰＥＢ（Post Exposure Bake））を施してもよい。 When the first photosensitive layer and the second photosensitive layer are formed on a transparent substrate using a transfer film, pattern exposure may be performed before the temporary support is peeled off, and then the temporary support may be peeled off. After exfoliating the body, pattern exposure may be performed.
In this step, the first photosensitive layer and the second photosensitive layer may be subjected to a heat treatment (so-called PEB (Post Exposure Bake)) after the pattern exposure and before the patterning step (that is, before the development). Good.
（パターン化工程）
　パターン化工程は、上記の光照射工程で光照射が行われた後の透明基材の両方の側を現像処理することで、透明基材の両方の側にそれぞれ異なるパターンを形成する。 (Patterning process)
In the patterning step, different patterns are formed on both sides of the transparent base material by developing both sides of the transparent base material after the light irradiation is performed in the light irradiation step.
　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、特に制約はなく、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、現像液は未露光の感光性樹脂層を溶解しうる現像液が好ましく、例えば、ｐＫａ＝７～１３の化合物（例えば、炭酸ナトリウム、水酸化カリウムなど）を０．０５ｍｏｌ／Ｌ～５ｍｏｌ／Ｌの濃度で含む現像液が好ましい。より具体的には、炭酸ナトリウム水溶液、水酸化カリウム水溶液などが挙げられる。
　現像液には、更に水と混和性を有する有機溶剤を少量添加してもよい。水と混和性を有する有機溶剤としては、メタノール、エタノール、２－プロパノール、１－プロパノール、ブタノール、ジアセトンアルコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノ－ｎ－ブチルエーテル、ベンジルアルコール、アセトン、メチルエチルケトン、シクロヘキサノン、ε－カプロラクトン、γ－ブチロラクトン、ジメチルホルムアミド、ジメチルアセトアミド、ヘキサメチルホスホルアミド、乳酸エチル、乳酸メチル、ε－カプロラクタム、Ｎ－メチルピロリドン等を挙げることができる。有機溶剤の濃度は０．１質量％～３０質量％が好ましい。
　また、現像液には、更に公知の界面活性剤を添加することができる。界面活性剤の濃度は０．０１質量％～１０質量％が好ましい。 Development can be performed using a developer.
The developer is not particularly limited, and a known developer such as a developer described in JP-A-5-72724 can be used. The developing solution is preferably a developing solution capable of dissolving the unexposed photosensitive resin layer. For example, a compound having a pKa of 7 to 13 (eg, sodium carbonate, potassium hydroxide, etc.) is added in an amount of 0.05 mol / L to 5 mol / L. A developer containing a concentration of L is preferred. More specifically, an aqueous solution of sodium carbonate, an aqueous solution of potassium hydroxide and the like can be mentioned.
A small amount of an organic solvent miscible with water may be added to the developer. Examples of water-miscible organic solvents include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone, and the like. The concentration of the organic solvent is preferably from 0.1% by mass to 30% by mass.
Further, a known surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.
　現像の方式としては、パドル現像、シャワー現像、シャワー現像とスピン現像との組み合わせ、ディップ現像等のいずれの方式でもよい。
　シャワー現像による場合は、露光後の第１感光層及び第２感光層に現像液をシャワーにより吹き付けることにより、未硬化部分を除去することで、パターン状の硬化物を形成することができる。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℃が好ましく、また、現像液のｐＨは８～１３が好ましい。 As a development method, any method such as paddle development, shower development, a combination of shower development and spin development, and dip development may be used.
In the case of shower development, a developer is sprayed on the exposed first and second photosensitive layers by a shower to remove uncured portions, whereby a patterned cured product can be formed. After the development, it is preferable to remove a development residue while spraying a detergent or the like with a shower and rubbing with a brush or the like.
The temperature of the developer is preferably from 20 ° C. to 40 ° C., and the pH of the developer is preferably from 8 to 13.
　以下に、本開示のパターン形成方法の一例を図４を参照して説明する。
　まず図４（ａ）に示すように、本開示の転写フィルム４１を透明基材２１の一方の側に貼り合わせ（貼り合わせ工程）、更に透明基材２１の他方の側に、本開示の転写フィルム４１とは異なる他の転写フィルム４３を貼り合わせ（第２感光層形成工程）、例えば図３に示す積層構造を有する積層体を準備する。
　そして、図４（ｂ）のように、透明基材２１からみて、積層体の転写フィルム４１を有する側に第１のフォトマスク３１を配置し、積層体の転写フィルム４３を有する側に第１のフォトマスク３１とはパターンが異なる第２のフォトマスク３３を配置し、それぞれのフォトマスクを介して積層体の両側から光照射する（光照射工程）。このとき、第１感光層１７と第２感光層２７とにはそれぞれ異なるパターン露光が行われる。
　続いて、第１のフォトマスク３１及び第２のフォトマスク３３を取り外し、更に積層体の両側に配置されている仮支持体１９、１９ａをそれぞれ剥離する。その後、積層体の両側に露出した第１感光層１７及び第２感光層２７に対して現像処理を施す（パターン化工程）。これにより、第１感光層１７のうち、第１のフォトマスク３１によってパターン露光されなかった領域は、現像除去される。また、遮光層１９のうち、上記パターン露光されなかった領域の下に位置する領域も除去される。これにより、図４（ｃ）に示すように、パターン露光された第１感光層１７ａ及びその下層である遮光層１３ａによってパターンが形成される。また同様に、第２感光層２７のうち、第２のフォトマスク３３によってパターン露光されなかった部分は、現像除去される。これにより、パターン露光された第２感光層２７ａによってパターンが形成される。
　このようにして、積層体の両側に光照射することにより、一方の側に照射された光が他方の側に侵入して他方の側の感光層へ与える影響が効果的に抑えられているので、透明基材の両側に互いにパターン形状の異なるパターンを、それぞれ精細に形成することができる。 Hereinafter, an example of the pattern forming method of the present disclosure will be described with reference to FIG.
First, as shown in FIG. 4A, the transfer film 41 of the present disclosure is attached to one side of the transparent substrate 21 (attaching step), and the transfer film 41 of the present disclosure is further attached to the other side of the transparent substrate 21. A transfer film 43 different from the film 41 is attached (second photosensitive layer forming step), and a laminate having a laminate structure shown in FIG. 3 is prepared, for example.
Then, as shown in FIG. 4B, the first photomask 31 is disposed on the side of the laminate including the transfer film 41, and the first photomask 31 is disposed on the side of the laminate including the transfer film 43. A second photomask 33 having a different pattern from that of the photomask 31 is arranged, and light is irradiated from both sides of the stacked body via the respective photomasks (light irradiation step). At this time, different pattern exposures are performed on the first photosensitive layer 17 and the second photosensitive layer 27, respectively.
Subsequently, the first photomask 31 and the second photomask 33 are removed, and the temporary supports 19 and 19a disposed on both sides of the stacked body are respectively peeled off. After that, the first photosensitive layer 17 and the second photosensitive layer 27 exposed on both sides of the laminate are subjected to a developing process (patterning step). As a result, areas of the first photosensitive layer 17 that have not been pattern-exposed by the first photomask 31 are developed and removed. Further, of the light-shielding layer 19, a region located below the region where the pattern is not exposed is also removed. Thereby, as shown in FIG. 4C, a pattern is formed by the pattern-exposed first photosensitive layer 17a and the light-shielding layer 13a as a lower layer. Similarly, portions of the second photosensitive layer 27 that have not been pattern-exposed by the second photomask 33 are developed and removed. As a result, a pattern is formed by the pattern-exposed second photosensitive layer 27a.
In this way, by irradiating light to both sides of the laminate, the light irradiated to one side is effectively suppressed from entering the other side and affecting the photosensitive layer on the other side. In addition, patterns having different pattern shapes can be formed finely on both sides of the transparent base material.
　本開示のパターン形成方法は、タッチパネル用電極及びタッチパネル用配線の少なくとも一方の形成に好適に用いられる。 パ タ ー ン The pattern forming method of the present disclosure is suitably used for forming at least one of an electrode for a touch panel and a wiring for a touch panel.
　以下に実施例を挙げて本発明をさら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、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されない。
　また、特に断りのない限り、「部」は質量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.
Unless otherwise specified, “parts” are based on mass.
（実施例１）
＜転写フィルムＡの作製＞
　仮支持体（ルミラー（登録商標）１６ＱＳ６２（厚み１６μｍ）、東レ株式会社；ポリエチレンテレフタレートフィルム）上に、下記組成の第１感光層形成用組成物Ｂ－１をスリット状ノズルを用いて塗布し、１００℃の熱風で２分間乾燥させて、乾燥厚み６μｍの第１感光層を形成した。
　なお、表１中、「重合体」は本開示におけるバインダーポリマーのことであり、「ラジカル重合性化合物」は本開示における重合性化合物のことである。 (Example 1)
<Preparation of transfer film A>
A first photosensitive layer forming composition B-1 having the following composition was coated on a temporary support (Lumilar (registered trademark) 16QS62 (thickness: 16 μm), Toray Industries, Inc .; polyethylene terephthalate film) using a slit nozzle. It was dried with hot air at 100 ° C. for 2 minutes to form a first photosensitive layer having a dry thickness of 6 μm.
In Table 1, “Polymer” refers to a binder polymer according to the present disclosure, and “radical polymerizable compound” refers to a polymerizable compound according to the present disclosure.
－第１感光層形成用組成物Ｂ－１－
Figure JPOXMLDOC01-appb-T000002
 -Composition B-1 for forming first photosensitive layer-
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　上記の重合体Ａ－１及びアクリベースＦＦ１８７における各構成単位の比は、モル比である。また、Ｍｅはメチル基を表す。 比 The ratio of each structural unit in the polymer A-1 and Acrybase FF187 is a molar ratio. Me represents a methyl group.
　次いで、第１感光層の上に、下記組成の中間層形成用組成物Ｃ－１をスリット状ノズルを用いて塗布し、１００℃の熱風で２分間乾燥させて、乾燥厚み１μｍの中間層を形成した。 Next, on the first photosensitive layer, a composition C-1 for forming an intermediate layer having the following composition was applied using a slit-shaped nozzle, and dried with hot air at 100 ° C. for 2 minutes to form an intermediate layer having a dry thickness of 1 μm. Formed.
－中間層形成用組成物Ｃ－１－
Figure JPOXMLDOC01-appb-T000004
 -Composition C-1 for forming an intermediate layer-
Figure JPOXMLDOC01-appb-T000004
　次いで、中間層上に、下記表３に記載の組成の遮光層形成用組成物Ａ－１をスリット状ノズルを用いて塗布し、１００℃の熱風で２分間乾燥させて、乾燥厚み３μｍの遮光層を形成した。 Then, a composition A-1 for forming a light-shielding layer having the composition shown in Table 3 below was applied to the intermediate layer using a slit-shaped nozzle, and dried with hot air at 100 ° C. for 2 minutes to form a light-shielding layer having a dry thickness of 3 μm. A layer was formed.
　更に、遮光層の上に保護フィルム（トレファン（登録商標）１２ＫＷ３７（厚み１２μｍ）、東レ株式会社；ポリプロピレンフィルム）を貼り合わせ、仮支持体／第１感光層／中間層／遮光層／保護フィルムの積層構造を有する転写フィルムＡを作製した。 Further, a protective film (Trefane (registered trademark) 12KW37 (thickness: 12 μm), Toray Industries, Inc .; polypropylene film) is laminated on the light-shielding layer, and the temporary support / first photosensitive layer / intermediate layer / light-shielding layer / protective film A transfer film A having a laminated structure of was prepared.
＜転写フィルムＢの作製＞
　次に、仮支持体（ルミラー（登録商標）１６ＱＳ６２（厚み１６μｍ）、東レ株式会社）上に、上記と同じ第１感光層形成用組成物Ｂ－１をスリット状ノズルを用いて塗布し、１００℃の熱風で２分間乾燥させて、乾燥厚み６μｍの第２感光層を形成した。形成された第２感光層の上に、更に、保護フィルム（トレファン（登録商標）１２ＫＷ３７（厚み１２μｍ）、東レ株式会社）を貼り合わせ、仮支持体／第２感光層／保護フィルムの積層構造を有する転写フィルムＢを作製した。 <Preparation of transfer film B>
Next, the same first photosensitive layer forming composition B-1 as described above was applied on a temporary support (Lumirror (registered trademark) 16QS62 (16 μm thickness, Toray Industries, Inc.) using a slit nozzle. The resultant was dried with hot air of 2 ° C. for 2 minutes to form a second photosensitive layer having a dry thickness of 6 μm. A protective film (Trefane (registered trademark) 12KW37 (thickness: 12 μm), Toray Industries, Inc.) is further laminated on the formed second photosensitive layer to form a laminated structure of temporary support / second photosensitive layer / protective film. Was produced.
＜パターン形成＞
－積層体の作製－
　まず初めに、以下のようにして積層体を作製した。
　上記のようにして作製した転写フィルムＡ（＝仮支持体／第１感光層／中間層／遮光層／保護フィルム；本開示の転写フィルム）を、５ｃｍ×５ｃｍ四方のサイズに裁断してフィルム片とし、フィルム片の保護フィルムを剥がした。そして、保護フィルムの剥離により露出した遮光層の表面がシクロオレフィン樹脂フィルム基材（厚み：５０μｍ；以下、「ＣＯＰ基板」ともいう。）と接するように、フィルム片を上記ＣＯＰ基板の一方の面に重ね、以下の条件でラミネートした（貼り合わせ工程）。
　<ラミネート条件>
・ロール温度：１１０℃
・線圧：０．６ＭＰａ
・線速度（ラミネート速度）：２．０ｍ／分 <Pattern formation>
-Production of laminate-
First, a laminate was produced as follows.
The transfer film A prepared as described above (= temporary support / first photosensitive layer / intermediate layer / light-shielding layer / protective film; transfer film of the present disclosure) is cut into a 5 cm × 5 cm square film piece. Then, the protective film of the film piece was peeled off. Then, the film piece is placed on one side of the COP substrate such that the surface of the light-shielding layer exposed by peeling of the protective film is in contact with the cycloolefin resin film substrate (thickness: 50 μm; hereinafter, also referred to as “COP substrate”). And laminated under the following conditions (lamination step).
<Lamination conditions>
・ Roll temperature: 110 ° C
・ Line pressure: 0.6MPa
・ Linear speed (lamination speed): 2.0 m / min
　続いて、上記のようにして作製した転写フィルムＢ（＝仮支持体／第２感光層／保護フィルム；本開示の転写フィルム以外の転写材料）を、上記と同様に５ｃｍ×５ｃｍ四方のサイズに裁断してフィルム片とし、フィルム片の保護フィルムを剥がした。そして、保護フィルムの剥離により露出した第２感光層の表面がＣＯＰ基板と接するように、フィルム片を上記ＣＯＰ基板の他方の面に重ね、上記と同じ条件でラミネートした（第２感光層形成工程）。
　以上のようにして、仮支持体／第１感光層／中間層／遮光層／ＣＯＰ基板／第２感光層／仮支持体の積層構造を有する積層体を作製した。 Subsequently, the transfer film B (= temporary support / second photosensitive layer / protective film; transfer material other than the transfer film of the present disclosure) prepared as described above was reduced to a size of 5 cm × 5 cm square as described above. It was cut into a film piece, and the protective film of the film piece was peeled off. Then, a film piece was laminated on the other surface of the COP substrate so that the surface of the second photosensitive layer exposed by peeling off the protective film was in contact with the COP substrate, and was laminated under the same conditions as described above (second photosensitive layer forming step). ).
As described above, a laminate having a laminated structure of temporary support / first photosensitive layer / intermediate layer / light shielding layer / COP substrate / second photosensitive layer / temporary support was produced.
－パターン形成－
　次に、作製した積層体に対して、積層体の仮支持体を剥離しない状態のまま、互いに異なるパターンを有するマスクパターンを介して、超高圧水銀灯により積層体の両方の側からそれぞれ露光量１２０ｍＪ／ｃｍ２にて光照射した（光照射工程）。光照射後、１時間放置した。その後、積層体の両方の側に設けられている仮支持体をそれぞれ剥離し、ＣＯＰ基材の両方の側に現像処理を施した（パターン化工程）。
　このようにして、ＣＯＰ基材の一方の側にある第１感光層、中間層及び遮光層と、他方の側にある第２感光層と、を現像し、ＣＯＰ基材の両側に互いに異なるパターンをそれぞれ形成した。
　なお、現像は、現像液として、温度２９℃、ｐＨ１１．２の０．７質量％炭酸カリウム水溶液を用い、４５秒間のシャワー現像により行った。 -Pattern formation-
Next, an exposure amount of 120 mJ was applied to both sides of the laminated body from both sides of the laminated body by using an ultra-high pressure mercury lamp through a mask pattern having a different pattern without leaving the temporary support of the laminated body. / Cm 2 (light irradiation step). After the light irradiation, it was left for 1 hour. Thereafter, the temporary supports provided on both sides of the laminate were respectively peeled off, and development processing was performed on both sides of the COP substrate (patterning step).
In this way, the first photosensitive layer, the intermediate layer and the light-shielding layer on one side of the COP substrate and the second photosensitive layer on the other side are developed, and different patterns are formed on both sides of the COP substrate. Was formed respectively.
The development was performed by using a 0.7% by mass aqueous solution of potassium carbonate having a temperature of 29 ° C. and a pH of 11.2 as a developing solution by shower development for 45 seconds.
＜評価＞
　次に、現像前後における積層体に対し、以下の評価を行った。測定及び評価の結果は、下記表３に示す。 <Evaluation>
Next, the following evaluation was performed on the laminate before and after development. The results of the measurement and evaluation are shown in Table 3 below.
－１．露光後の残渣（かぶり）－
　透明基材から積層体の積層方向を見た場合に、積層体の、第１感光層側から光照射されなかった未照射領域（１０００μｍ×１０００μｍ四方）について、第１感光層側から光学顕微鏡にて倍率５倍で観察し、顕微鏡写真から残渣の面積を求め、第１感光層及び遮光層の透明基材上における残渣（かぶり）の面積率を算出した。そして、算出値をもとに以下の評価基準にしたがって評価した。
　残渣が認められる場合、第２感光層側からの照射光によって第１感光層又は遮光層が硬化したこと（即ち、露光かぶりが生じたこと）を示す。
　ここで、第１感光層の残渣は、遮光層の表面に残存する第１感光層の残渣を確認し、観察領域である未照射領域中に占める面積率を求めた。遮光層の遮光効果が低い場合、第１感光層は第２感光層側からの照射光により感光し、残渣が生じやすくなる。
　また、遮光層の残渣は、透明基材の表面に残存する遮光層の残渣を確認し、観察領域である未照射領域中に占める面積率を求めた。遮光層の遮光効果が確保されても、遮光層自体が感光性を有する場合、遮光層自体が感光し、残渣が生じやすくなる。
　<評価基準>
Ａ：残渣が認められない。
Ｂ：残渣を確認でき、残渣の面積率が未照射領域の面積に対して５％以下である。
Ｃ：残渣を確認でき、残渣の面積率が未照射領域の面積に対して５％超１０％以下である。
Ｄ：残渣を確認でき、残渣の面積率が未照射領域の面積に対して１０％超３０％以下である。
Ｅ：残渣を確認でき、残渣の面積率が未照射領域の面積に対して３０％を超えている。 -1. Residue after exposure (fog)
When viewed from the transparent substrate in the laminating direction of the laminate, an unirradiated area (1000 μm × 1000 μm square) of the laminate which was not irradiated with light from the first photosensitive layer side was subjected to an optical microscope from the first photosensitive layer side. Then, the area of the residue was determined from the micrograph, and the area ratio of the residue (fogging) on the transparent substrate of the first photosensitive layer and the light-shielding layer was calculated. And it evaluated according to the following evaluation criteria based on the calculated value.
When a residue is observed, it indicates that the first photosensitive layer or the light-shielding layer has been cured by irradiation light from the second photosensitive layer side (that is, exposure fog has occurred).
Here, as for the residue of the first photosensitive layer, the residue of the first photosensitive layer remaining on the surface of the light-shielding layer was confirmed, and the area ratio occupied in the unirradiated region, which is the observation region, was determined. When the light-shielding effect of the light-shielding layer is low, the first photosensitive layer is exposed to irradiation light from the second photosensitive layer side, and a residue is easily generated.
As for the residue of the light-shielding layer, the residue of the light-shielding layer remaining on the surface of the transparent substrate was confirmed, and the area ratio occupied in the unirradiated region, which is the observation region, was determined. Even if the light-blocking effect of the light-blocking layer is ensured, if the light-blocking layer itself has photosensitivity, the light-blocking layer itself is exposed to light and residues are likely to be generated.
<Evaluation criteria>
A: No residue is observed.
B: Residue can be confirmed, and the area ratio of the residue is 5% or less with respect to the area of the unirradiated region.
C: Residue was confirmed, and the area ratio of the residue was more than 5% and 10% or less based on the area of the unirradiated region.
D: Residue can be confirmed, and the area ratio of the residue is more than 10% and 30% or less with respect to the area of the unirradiated region.
E: Residue was confirmed, and the area ratio of the residue exceeded 30% of the area of the unirradiated region.
－２．遮光層の光学濃度（ＯＤ）－
　仮支持体（ルミラー１６ＱＳ６２；厚み１６μｍ）上に遮光層形成用組成物Ａ－１をスリット状ノズルを用いて塗布し、温度１００℃のコンベクションオーブンで２分間乾燥させて厚み３μｍの遮光層を形成した後、遮光層の上に更に保護フィルム（トレファン１２ＫＷ３７）を貼り合わせ、仮支持体／遮光層／保護フィルムの積層構造の転写フィルムを作製した。
　この転写フィルムを５ｃｍ×５ｃｍ使用のサイズにカットして測定用フィルム片とし、測定用フィルム片から保護フィルムを剥がした。そして、保護フィルムの剥離により露出した遮光層の表面がガラス基材と接すように、測定用フィルム片をガラスに重ね、上記と同様の条件でガラス基材（Ｅａｇｌｅ　ＸＧ（厚み０．７ｍｍ）、コーニング社製）にラミネートして、仮支持体／遮光層／ガラス基材の積層構造を有する積層体を得た。
　この積層体の遮光層の光学濃度を、透過濃度計（ＢＭＴ－１、サカタインクスエンジニアリング社製）を用いて測定した。
　更に、積層体の作製に使用した仮支持体及びガラス基材の光学濃度を上記と同様の方法で測定した。
　そして、積層体の光学濃度から仮支持体及びガラス基材の光学濃度を減算し、遮光層の光学濃度とした。測定結果を下記表３に示す。 -2. Optical density (OD) of light shielding layer
A composition A-1 for forming a light-shielding layer is applied on a temporary support (Lumirror 16QS62; thickness 16 μm) using a slit-shaped nozzle, and dried in a convection oven at a temperature of 100 ° C. for 2 minutes to form a light-shielding layer having a thickness of 3 μm. After that, a protective film (Trefane 12KW37) was further stuck on the light-shielding layer to prepare a transfer film having a laminated structure of temporary support / light-shielding layer / protective film.
This transfer film was cut into a size of 5 cm x 5 cm to form a film piece for measurement, and the protective film was peeled off from the film piece for measurement. Then, the film piece for measurement is superimposed on the glass so that the surface of the light-shielding layer exposed by peeling of the protective film is in contact with the glass substrate, and the glass substrate (Eagle XG (thickness 0.7 mm)) is formed under the same conditions as above. (Manufactured by Corning Incorporated)) to obtain a laminate having a laminated structure of temporary support / light-shielding layer / glass substrate.
The optical density of the light-shielding layer of this laminate was measured using a transmission densitometer (BMT-1, manufactured by Sakata Inx Engineering).
Further, the optical densities of the temporary support and the glass substrate used for producing the laminate were measured in the same manner as described above.
Then, the optical density of the temporary support and the glass substrate was subtracted from the optical density of the laminate to obtain the optical density of the light-shielding layer. The measurement results are shown in Table 3 below.
（実施例２～４、比較例１）
　実施例１において、遮光層形成用組成物Ａ－１を、表３に示す遮光層形成用組成物Ａ－２～Ａ－４又はＡＡ－１に代えたこと以外は、実施例１と同様にして、転写フィルムを作製し、同様の測定及び評価を行った。測定及び評価の結果は、下記表３に示す。 (Examples 2 to 4, Comparative Example 1)
Example 1 was repeated in the same manner as in Example 1 except that the composition A-1 for forming a light-shielding layer was changed to the compositions A-2 to A-4 or AA-1 for forming a light-shielding layer shown in Table 3. Then, a transfer film was prepared and the same measurement and evaluation were performed. The results of the measurement and evaluation are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表３に示すように、本開示の転写フィルムを用いた実施例１～４では、一定の光学濃度を有する遮光層の付設により遮光効果が得られたため、透明基材の両側にそれぞれ光照射を行っても、一方の側が他方の側の照射光の影響を受けにくく、透明基材の両側に精細なパターンを形成することができた。この中で、実施例３は、遮光層が光重合開始剤を含有するため、遮光層による遮光効果によって第１感光層は感光せず残渣が少なく抑えられたものの、遮光層の重合反応が僅かに進行した結果、遮光層の残渣が多少認められた。
　これに対し、光学濃度が低い遮光層を付設した比較例１では、遮光効果が足りず、透明基材の両側にそれぞれ光照射を行った場合に一方の側の照射光が他方の側へ透過してしまい、一方の側が他方の側の照射光の影響を受ける結果を招き、透明基材の両側において残渣が著しく発生した。 As shown in Table 3, in Examples 1 to 4 using the transfer film of the present disclosure, a light-shielding effect was obtained by providing a light-shielding layer having a constant optical density. Even if it was performed, one side was hardly affected by the irradiation light on the other side, and a fine pattern could be formed on both sides of the transparent substrate. Among them, in Example 3, since the light-shielding layer contained a photopolymerization initiator, the first photosensitive layer was not exposed due to the light-shielding effect of the light-shielding layer and the residue was suppressed to a small extent, but the polymerization reaction of the light-shielding layer was slight. As a result, some residue of the light-shielding layer was observed.
In contrast, in Comparative Example 1 in which a light-shielding layer having a low optical density was provided, the light-shielding effect was insufficient, and when light irradiation was performed on both sides of the transparent base material, the irradiation light on one side was transmitted to the other side. As a result, one side was affected by the irradiation light on the other side, resulting in significant generation of residues on both sides of the transparent substrate.
（実施例５～６）
　実施例１において、中間層形成用組成物Ｃ－１を、表４に示す中間層形成用組成物Ｃ～２又はＣ～３に代えたこと以外は、実施例１と同様にして、転写フィルムを作製し、同様の測定及び評価を行った。測定及び評価の結果は、下記表５に示す。 (Examples 5 and 6)
A transfer film was obtained in the same manner as in Example 1 except that the composition C-1 for forming an intermediate layer in Example 1 was changed to the compositions C-2 or C-3 for forming an intermediate layer shown in Table 4. Was prepared, and similar measurements and evaluations were performed. The results of the measurement and evaluation are shown in Table 5 below.
－中間層形成用組成物Ｃ－２、Ｃ－３－
Figure JPOXMLDOC01-appb-T000006
 -Compositions C-2 and C-3- for forming an intermediate layer
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表５に示すように、本開示の転写フィルムを用いた実施例５～６では、一定の光学濃度を有する遮光層の付設により遮光効果が得られたため、透明基材の両側にそれぞれ光照射を行っても、一方の側が他方の側の照射光の影響を受けにくく、透明基材の両側に精細なパターンを形成することができた。 As shown in Table 5, in Examples 5 and 6 using the transfer film of the present disclosure, a light-shielding effect was obtained by providing a light-shielding layer having a constant optical density. Even if it was performed, one side was hardly affected by the irradiation light on the other side, and a fine pattern could be formed on both sides of the transparent substrate.
　なお、２０１８年８月２３日に出願された日本国特許出願２０１８－１５６４１９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。また、本明細書に記載された全ての文献、特許出願および技術規格は、個々の文献、特許出願、およ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. 2018-156419 filed on August 23, 2018 is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards described herein are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference. , Incorporated herein by reference.

Claims (14)

  1. 　仮支持体と、
    　バインダーポリマー、重合性化合物、及び光重合開始剤を含む第１感光層と、
    　少なくともバインダーポリマーを含み、かつ、光学濃度が０．５以上である遮光層と、
    　をこの順に有する転写フィルム。     A temporary support,
    A first photosensitive layer containing a binder polymer, a polymerizable compound, and a photopolymerization initiator,
    A light-shielding layer containing at least a binder polymer and having an optical density of 0.5 or more,
    A transfer film having in this order.
  2. 　前記遮光層が、更に、紫外線吸収材料を含む請求項１に記載の転写フィルム。 The transfer film according to claim 1, wherein the light shielding layer further contains an ultraviolet absorbing material.
  3. 　前記紫外線吸収材料が、カーボンブラックを含む請求項２に記載の転写フィルム。 The transfer film according to claim 2, wherein the ultraviolet absorbing material contains carbon black.
  4. 　前記遮光層が、更に、重合性化合物を含む請求項１～請求項３のいずれか１項に記載の転写フィルム。 (4) The transfer film according to any one of (1) to (3), wherein the light-shielding layer further contains a polymerizable compound.
  5. 　光重合開始剤の含有量が、前記遮光層の全固形分量に対して、１質量％以下である請求項１～請求項４のいずれか１項に記載の転写フィルム。 (5) The transfer film according to any one of (1) to (4), wherein the content of the photopolymerization initiator is 1% by mass or less based on the total solid content of the light shielding layer.
  6. 　前記第１感光層と前記遮光層との間に、中間層を有する請求項１～請求項５のいずれか１項に記載の転写フィルム。　 The transfer film according to any one of claims 1 to 5, wherein an intermediate layer is provided between the first photosensitive layer and the light-shielding layer.
  7. 　前記中間層が、水又は炭素数１～４の低級アルコールに対して可溶性を有するバインダーポリマーを含む請求項６に記載の転写フィルム。 The transfer film according to claim 6, wherein the intermediate layer contains a binder polymer having solubility in water or a lower alcohol having 1 to 4 carbon atoms.
  8. 　前記中間層が、更に、重合性化合物及び光重合開始剤を含む請求項６又は請求項７に記載の転写フィルム。 The transfer film according to claim 6, wherein the intermediate layer further contains a polymerizable compound and a photopolymerization initiator.
  9. 　透明基材と、
    　請求項１～請求項８のいずれか１項に記載の転写フィルムと、
    を有する積層体。     A transparent substrate,
    A transfer film according to any one of claims 1 to 8,
    A laminate having:
  10. 　前記透明基材の、前記転写フィルムが積層された側と反対側に、第２感光層を有する請求項９に記載の積層体。 The laminated body according to claim 9, wherein a second photosensitive layer is provided on a side of the transparent substrate opposite to a side on which the transfer film is laminated.
  11. 　前記第２感光層が、バインダーポリマー、重合性化合物、及び光重合開始剤を含有する請求項１０に記載の積層体。 The laminate according to claim 10, wherein the second photosensitive layer contains a binder polymer, a polymerizable compound, and a photopolymerization initiator.
  12. 　透明基材の一方の側に、請求項１～請求項８のいずれか１項に記載の転写フィルムを貼り合わせる工程と、
    　前記透明基材の他方の側に、バインダーポリマー、重合性化合物、及び光重合開始剤を含む第２感光層を形成する工程と、
    　前記透明基材の両方の側に対して、光をそれぞれ異なるパターンにて照射する工程と、
    　前記照射が行われた後の前記透明基材の両方の側を現像処理することで、前記透明基材の両方の側にそれぞれ異なるパターンを形成する工程と、
    　を有するパターン形成方法。     A step of attaching the transfer film according to any one of claims 1 to 8 to one side of a transparent substrate,
    Forming a second photosensitive layer containing a binder polymer, a polymerizable compound, and a photopolymerization initiator on the other side of the transparent substrate;
    For both sides of the transparent substrate, a step of irradiating light in different patterns,
    By developing both sides of the transparent substrate after the irradiation is performed, a step of forming a different pattern on each side of the transparent substrate,
    A pattern forming method comprising:
  13. 　前記透明基材は、両方の面に金属電極及び金属配線の少なくとも一方を有する請求項１２に記載のパターン形成方法。 The pattern forming method according to claim 12, wherein the transparent substrate has at least one of a metal electrode and a metal wiring on both surfaces.
  14. 　タッチパネル用電極及びタッチパネル用配線の少なくとも一方の形成に用いられる請求項１２又は請求項１３に記載のパターン形成方法。 14. The pattern forming method according to claim 12, which is used for forming at least one of an electrode for a touch panel and a wiring for a touch panel.
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