WO2020040054A1 - 転写フィルム、積層体、及びパターン形成方法 - Google Patents

転写フィルム、積層体、及びパターン形成方法 Download PDF

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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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light
mass
photosensitive layer
transfer film
shielding layer
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PCT/JP2019/032150
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English (en)
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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Priority to CN201980042030.XA priority Critical patent/CN112352199A/zh
Priority to JP2020538358A priority patent/JP7094372B2/ja
Publication of WO2020040054A1 publication Critical patent/WO2020040054A1/ja

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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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