WO2023026786A1 - Film de transfert et procédé de production de stratifié - Google Patents

Film de transfert et procédé de production de stratifié Download PDF

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Publication number
WO2023026786A1
WO2023026786A1 PCT/JP2022/029588 JP2022029588W WO2023026786A1 WO 2023026786 A1 WO2023026786 A1 WO 2023026786A1 JP 2022029588 W JP2022029588 W JP 2022029588W WO 2023026786 A1 WO2023026786 A1 WO 2023026786A1
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compound
photosensitive layer
transfer film
carboxy group
mass
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PCT/JP2022/029588
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English (en)
Japanese (ja)
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秀之 中村
圭吾 山口
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富士フイルム株式会社
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Priority to JP2023543772A priority Critical patent/JPWO2023026786A1/ja
Publication of WO2023026786A1 publication Critical patent/WO2023026786A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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

Definitions

  • the present invention relates to a method for manufacturing a transfer film and a laminate.
  • Photolithography is a common method for forming fine structures.
  • a temporary support and a photosensitive layer formed using a photosensitive material arranged on the temporary support are used.
  • a method using a transfer film having a Examples of the method of forming a pattern using a transfer film include a method of exposing and developing a photosensitive layer transferred from the transfer film onto an arbitrary base material through a mask having a predetermined pattern shape. be done.
  • Patent Document 1 discloses a method of using a resin transfer material (transfer film) containing a colorant as a method of manufacturing a color filter for a liquid crystal display device.
  • the present inventors transferred the transfer film containing the colorant described in Patent Document 1 to a substrate, and the color of the colored layer obtained by exposing the resin layer of the colored photosensitive resin composition containing the colorant. Upon examination, it was found that the tint derived from the coloring agent was difficult to visually recognize, and improvement was required.
  • the present invention has a temporary support and a colored layer containing a coloring agent disposed on the temporary support, the layer containing the colored layer on the temporary support is transferred to the substrate, exposed and developed.
  • An object of the present invention is to provide a transfer film in which the color derived from the coloring agent on the base material is easily visible.
  • Another object of the present invention is to provide a method for producing a laminate using the transfer film.
  • the present inventor has completed the present invention as a result of diligent studies aimed at solving the above problems. That is, the inventors have found that the above problems can be solved by the following configuration.
  • Requirement (V1) The photosensitive layer contains a compound A having a carboxy group, and a compound ⁇ having a structure that reduces the amount of the carboxy group contained in the compound A upon exposure.
  • the photosensitive layer contains a compound A having a carboxy group, and the compound A further contains a structure that reduces the amount of the carboxy group contained in the compound A upon exposure.
  • the compound ⁇ is a compound B having a structure capable of accepting electrons from the carboxy group contained in the compound A in a photoexcited state
  • the transfer film according to [2] wherein in the requirement (W1), the structure is a structure capable of accepting electrons from the carboxy group contained in the compound A in a photoexcited state.
  • the photosensitive layer satisfies the requirement (V1), and the total number of the electron-accepting structures contained in the compound B in the photosensitive layer is equal to the total number of carboxy groups contained in the compound A.
  • the transfer film according to [4] which is 1 mol % or more.
  • the present invention has a temporary support and a colored layer containing a coloring agent disposed on the temporary support, the layer containing the colored layer on the temporary support is transferred to a substrate, and exposure and development are performed. It is possible to provide a transfer film in which the color derived from the coloring agent on the base material is easily visible when the transfer film is applied. Moreover, according to this invention, the manufacturing method of the laminated body using the said transfer film can also be provided.
  • FIG. 1 is a side view showing an example of a laminate of the present invention
  • a numerical range represented by "to” means a range including the numerical values before and after “to” as lower and upper limits.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of the numerical range described in other steps. good.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the values shown in the examples.
  • step in this specification is not only an independent step, but even if it cannot be clearly distinguished from other steps, if the intended purpose of the step is achieved included.
  • transparent means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more. Therefore, for example, a “transparent resin layer” refers to a resin layer having an average transmittance of 80% or more for visible light with a wavelength of 400 to 700 nm. Also, the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
  • actinic ray or “radiation” means, for example, g-line, h-line, and i-line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X ray, electron beam (EB), and the like.
  • light means actinic rays or radiation.
  • exposure means not only exposure by far ultraviolet rays, extreme ultraviolet rays, X-rays, and EUV light typified by mercury lamps and excimer lasers, but also electron beams, ion beams, and the like. lithography by particle beam is also included in the exposure.
  • the content ratio of each structural unit of the polymer is a molar ratio.
  • the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.
  • the molecular weight when there is a molecular weight distribution is the weight average molecular weight.
  • the weight average molecular weight of the resin is the weight average molecular weight obtained by gel permeation chromatography (GPC) in terms of polystyrene.
  • (meth)acrylic acid is a concept that includes both acrylic acid and methacrylic acid
  • (meth)acryloyl group is a concept that includes both acryloyl and methacryloyl groups.
  • the thickness of a layer is the average thickness measured using a scanning electron microscope (SEM) for thicknesses of 0.5 ⁇ m or more, and less than 0.5 ⁇ m. is the average thickness measured using a transmission electron microscope (TEM).
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the average thickness is an average thickness obtained by forming a section to be measured using an ultramicrotome, measuring the thickness at arbitrary five points, and arithmetically averaging them.
  • the transfer film of the present invention has a temporary support, a photosensitive layer containing a compound A having a carboxy group (hereinafter also simply referred to as "compound A”), and a colored layer containing a coloring agent in this order.
  • a feature of the transfer film of the present invention is that the content of the carboxy groups in the photosensitive layer is reduced by exposure to actinic rays or radiation (hereinafter also referred to as "exposure").
  • the transfer film of the present invention transfers a layer containing a colored layer on a temporary support to a substrate, and when exposed and developed, the mechanism by which the color derived from the coloring agent is easily visible is not necessarily clear.
  • the inventors presume as follows.
  • the photosensitive layer and the colored layer contained in the transfer film of the present invention are transferred to a base material, and the base material on which the photosensitive layer and the colored layer are laminated is exposed in a pattern and developed.
  • fine protrusions can be formed and that the protrusions tend to have a forward tapered shape. More specifically, when the photosensitive layer is exposed in a pattern, as will be described later in FIG. As a result, the presence of such protrusions suppresses the reflection of light incident from the protrusion side, making it easier to visually recognize the color derived from the coloring agent. Details will be described later.
  • the photosensitive layer and the colored layer contained in the transfer film are transferred to the base material, the photosensitive layer is exposed to form a laminate including a pattern consisting of a plurality of projections.
  • the visibility of color is also called “color visibility”.
  • excellent color visibility when the color derived from the coloring agent is more easily visible in the laminate obtained by the above procedure, it is also referred to as "excellent color visibility”.
  • the transfer film of the present invention has a temporary support, a photosensitive layer containing a compound A having a carboxy group, and a colored layer containing a coloring agent in this order, and contains a carboxy group by irradiation with actinic rays or radiation. decrease in volume.
  • An example of the structure of the transfer film of the present invention is shown in FIG.
  • the transfer film 10 shown in FIG. 1 has a temporary support 12, a photosensitive layer 14, and a colored layer 16 in this order. Other layers may be provided between the photosensitive layer 14 and the temporary support 12 and/or between the photosensitive layer 14 and the colored layer 16 .
  • a cover film may be provided on the surface of the colored layer 16 opposite to the photosensitive layer 14 .
  • Each layer of the transfer film will be described in detail below.
  • the temporary support is a support that supports the photosensitive layer and is peelable from the photosensitive layer.
  • the temporary support preferably has light transmittance in that the photosensitive layer can be exposed through the temporary support when patternwise exposing the photosensitive layer.
  • pattern exposure is a form of exposure in a pattern, and means exposure in a form in which an exposed portion and an unexposed portion are present.
  • having light transmittance means that the transmittance of the dominant wavelength of light used for exposure (either pattern exposure or overall exposure) is 50% or more.
  • the transmittance of the dominant wavelength of light used for exposure is preferably 60% or more, more preferably 70% or more, from the viewpoint of better exposure sensitivity.
  • a method of measuring transmittance a method of measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd. can be mentioned.
  • the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is preferable because of its superior strength, flexibility, and the like.
  • the resin film include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among them, a biaxially stretched polyethylene terephthalate film is preferred.
  • the number of particles, foreign substances, and defects contained in the temporary support is small.
  • the number of fine particles, foreign substances, and defects with a diameter of 2 ⁇ m or more is preferably 50/10 mm 2 or less, more preferably 10/10 mm 2 or less, and even more preferably 3/10 mm 2 or less. .
  • the lower limit is not particularly limited, it can be 1 piece/10 mm 2 or more.
  • the temporary support has a layer in which particles with a diameter of 0.5 to 5 ⁇ m are present at a rate of 1/mm 2 or more on the side opposite to the side on which the photosensitive layer is formed, in order to further improve handling properties. More preferably, particles with a diameter of 0.5 to 5 ⁇ m are present in an amount of 1 to 50/mm 2 .
  • the thickness of the temporary support is not particularly limited, and is preferably 5 to 200 ⁇ m, more preferably 10 to 150 ⁇ m, from the viewpoint of ease of handling and excellent versatility.
  • the thickness of the temporary support is appropriately selected according to the material, considering the strength of the support, the flexibility required for bonding with other substrates, and the light transmittance required in the first exposure step. can.
  • Preferred aspects of the temporary support include, for example, paragraphs 0017 to 0018 of JP-A-2014-085643, paragraphs 0019-0026 of JP-A-2016-027363, paragraphs 0041 to 0057 of WO2012/081680A1, and WO2018/ 179370A1, paragraphs 0029-0040, the contents of which are incorporated herein.
  • the temporary support for example, Cosmoshine (registered trademark) A4100 manufactured by Toyobo Co., Ltd., Lumirror (registered trademark) 16FB40 manufactured by Toray Industries, Inc., or Lumirror (registered trademark) 16QS62 manufactured by Toray Industries, Inc. is used.
  • particularly preferred embodiments of the temporary support include a 16 ⁇ m thick biaxially stretched polyethylene terephthalate film, a 12 ⁇ m thick biaxially stretched polyethylene terephthalate film, and a 9 ⁇ m thick biaxially stretched polyethylene terephthalate film.
  • the photosensitive layer contains compound A having a carboxy group (compound A), and has a mechanism whereby the content of the carboxy group derived from compound A is reduced by exposure.
  • the photosensitive layer preferably satisfies either requirement (V1) or requirement (W1) shown below, and more preferably satisfies requirement (V1).
  • the photosensitive layer may be a photosensitive layer that satisfies both the requirements (V1) and (W1).
  • specific structure S0 a structure having a structure that reduces the amount of carboxy groups contained in compound A upon exposure.
  • Requirement (W1) The photosensitive layer contains compound A having a carboxy group, and compound A further contains a structure (specific structure S0) that reduces the amount of carboxy groups contained in compound A upon exposure.
  • the compound ⁇ is preferably a compound B having a structure (hereinafter also referred to as “specific structure S1”) capable of accepting electrons from the carboxy group contained in the compound A in a photoexcited state.
  • the structure is preferably a structure (specific structure S1) capable of accepting electrons from the carboxy group contained in compound A in a photoexcited state.
  • the above-mentioned specific structure S0 is a structure that exhibits the action of reducing the amount of carboxy groups contained in compound A when exposed to light.
  • the specific structure S0 is preferably a structure that transitions from a ground state to an excited state upon exposure and exhibits an effect of reducing the number of carboxyl groups in compound A in the excited state.
  • Specific structure S0 includes, for example, a structure (specific structure S1 described later) that can accept electrons from a carboxy group contained in compound A upon being exposed to light and being photoexcited.
  • Photosensitive layer of embodiment X-1-a1 A photosensitive layer that satisfies either requirement (V1) or requirement (W1) and does not substantially contain a polymerizable compound different from the polymer described below and a photopolymerization initiator.
  • Photosensitive layer of embodiment X-1-a2 It is a photosensitive layer that satisfies either requirement (V1) or requirement (W1) and does not substantially contain a photopolymerization initiator.
  • - Photosensitive layer of embodiment X-1-a3 A photosensitive layer that satisfies either requirement (V1) or requirement (W1) and contains a polymerizable compound and a photopolymerization initiator.
  • substantially free of a polymerizable compound means that the content of the polymerizable compound is 3% by mass with respect to the total mass of the photosensitive layer. It may be less than, preferably 0 to 1% by mass, more preferably 0 to 0.1% by mass.
  • the phrase "substantially free of a photopolymerization initiator” means that the content of the photopolymerization initiator in the photosensitive layer It may be less than 0.1% by mass, preferably 0 to 0.05% by mass, more preferably 0 to 0.01% by mass, relative to the total mass of the.
  • the mechanism by which the content of carboxyl groups derived from compound A is reduced by exposure includes, for example, a decarboxylation method. It can be selected as appropriate. However, the reduction in the content of the carboxy group derived from compound A means that the carboxy group is eliminated as CO 2 , and does not include the change of the carboxy group to a group other than the carboxy group due to esterification or the like.
  • the components of the photosensitive layer are described below.
  • Compound A is a compound having a carboxy group.
  • Compound A may be a low-molecular compound or a high-molecular compound (hereinafter also referred to as "polymer”), but is preferably a polymer. That is, compound A is preferably a polymer having a carboxy group.
  • the molecular weight of compound A is preferably less than 5,000, more preferably 2,000 or less, even more preferably 1,000 or less, particularly preferably 500 or less, most preferably 400 or less. preferable.
  • the lower limit of the weight-average molecular weight of compound A is preferably 5,000 or more, more preferably 10,000 or more, and 15,000 or more, in terms of excellent formability of the photosensitive layer. is more preferred.
  • the upper limit is not particularly limited, it is preferably 50,000 or less from the viewpoint of better adhesion (laminate adhesion) when laminating (transferring) to any base material.
  • the polymer is preferably an alkali-soluble resin.
  • alkali-soluble means that the dissolution rate determined by the method below is 0.01 ⁇ m/second or more.
  • a propylene glycol monomethyl ether acetate solution having a target compound (e.g., polymer) concentration of 25% by mass is applied onto a glass substrate, and then heated in an oven at 100 ° C. for 3 minutes to form a coating film of the target compound ( thickness 2.0 ⁇ m).
  • the dissolution rate ( ⁇ m/sec) of the coating film is determined by immersing the coating film in a 1% by mass sodium carbonate aqueous solution (liquid temperature: 30° C.).
  • the target compound does not dissolve in propylene glycol monomethyl ether acetate, the target compound is dissolved in an organic solvent other than propylene glycol monomethyl ether acetate having a boiling point of less than 200°C (eg, tetrahydrofuran, toluene, or ethanol).
  • an organic solvent other than propylene glycol monomethyl ether acetate having a boiling point of less than 200°C eg, tetrahydrofuran, toluene, or ethanol.
  • the carboxy group is a concept including both an anionized carboxy group (—COO ⁇ ) and a non-anionized carboxy group.
  • Compound A may contain a structure (specific structure S0) that reduces the amount of carboxy groups contained in compound A upon exposure.
  • compound A not containing specific structure S0 is also referred to as “compound Aa”
  • compound A containing specific structure S0 is also referred to as “compound Ab”.
  • the compound Ab is preferably a polymer. That is, compound Ab is preferably a polymer containing specific structure S0.
  • Compound A does not contain specific structure S0 means that compound A does not substantially contain specific structure S0.
  • the content of specific structure S0 in compound Aa is relative to the total mass of compound Aa The content is preferably less than 1% by mass, preferably 0 to 0.5% by mass, more preferably 0 to 0.05% by mass.
  • the content of the specific structure S0 in the compound Ab is preferably 1% by mass or more, more preferably 1 to 50% by mass, even more preferably 5 to 40% by mass, relative to the total mass of the compound Ab.
  • the content of compound Ab is preferably 5 to 100% by mass relative to the total mass of compound A.
  • the specific structure S0 is a structure that exhibits the effect of reducing the amount of carboxyl groups contained in compound A when exposed to light.
  • the specific structure S0 is preferably a structure that transitions from a ground state to an excited state upon exposure and exhibits an effect of reducing the number of carboxyl groups in compound A in the excited state.
  • Specific structure S0 of compound A includes a structure (specific structure S1) that can accept an electron from a carboxy group contained in compound A in a photoexcited state.
  • Such a specific structure S1 includes a heteroaromatic ring.
  • the heteroaromatic ring may be monocyclic or polycyclic, and is preferably polycyclic.
  • a polycyclic heteroaromatic ring is formed by condensing a plurality of (for example, 2 to 5) aromatic ring structures, and at least one of the plurality of aromatic ring structures has a heteroatom as a ring member atom. have.
  • the heteroaromatic ring has one or more heteroatoms (nitrogen atom, oxygen atom, sulfur atom, etc.) as ring member atoms, preferably 1 to 4 heteroatoms.
  • the heteroaromatic ring preferably has one or more (eg, 1 to 4) nitrogen atoms as ring member atoms.
  • the number of ring member atoms in the above heteroaromatic ring is preferably 5-15.
  • heteroaromatic ring examples include monocyclic heteroaromatic rings such as pyridine ring, pyrazine ring, pyrimidine ring, and triazine ring; bicyclic rings such as quinoline ring, isoquinoline ring, quinoxaline ring, and quinazoline ring; heteroaromatic ring condensed with ; a heteroaromatic ring condensed with three rings such as acridine ring, phenanthridine ring, phenanthroline ring, and phenazine ring.
  • monocyclic heteroaromatic rings such as pyridine ring, pyrazine ring, pyrimidine ring, and triazine ring
  • bicyclic rings such as quinoline ring, isoquinoline ring, quinoxaline ring, and quinazoline ring
  • heteroaromatic ring condensed with a heteroaromatic ring condensed with three rings such as acridine ring,
  • the heteroaromatic ring may have one or more (for example, 1 to 5) substituents, and examples of the substituents include alkyl groups, aryl groups, halogen atoms, acyl groups, alkoxycarbonyl groups, and arylcarbonyl groups. , carbamoyl, hydroxy, cyano, and nitro groups.
  • the aromatic ring has two or more substituents, the plurality of substituents may be combined to form a non-aromatic ring.
  • the heteroaromatic ring is directly bonded to the carbonyl group.
  • the heteroaromatic ring is bonded to the imide group to form a heteroaromatic imide group.
  • the imide group in the heteroaromatic imide group may or may not form an imide ring together with the heteroaromatic ring.
  • a series of aromatic ring structures linked by a structure selected from the group consisting of, and among the plurality of aromatic rings constituting the series of aromatic ring structures
  • the compound A having a carboxy group is preferably a monomer having a carboxy group (hereinafter also referred to as a "carboxy group-containing monomer”) or a polymer having a carboxy group (hereinafter also referred to as a "carboxy group-containing polymer”).
  • a carboxy group-containing polymer is more preferable in that the pattern forming ability of the photosensitive layer is more excellent and the film-forming property is more excellent.
  • compound A having a carboxy group may contain specific structure S0 (preferably specific structure S1).
  • the carboxy group-containing monomer and the carboxy group-containing polymer may contain specific structure S0 (preferably specific structure S1).
  • compound A having a carboxy group contains specific structure S0 (preferably specific structure S1), it is particularly preferably a carboxy group-containing polymer containing specific structure S0 (preferably specific structure S1).
  • the carboxy group-containing monomer and carboxy group-containing polymer are described below.
  • a polymerizable compound having a carboxy group and one or more (eg, 1 to 15) ethylenically unsaturated groups is preferred.
  • ethylenically unsaturated groups include (meth)acryloyl groups, vinyl groups, and styryl groups, with (meth)acryloyl groups being preferred.
  • a bifunctional or higher functional monomer having a carboxy group is preferable from the viewpoint of better film-forming properties.
  • the bifunctional or more functional monomer means a polymerizable compound having two or more (for example, 2 to 15) ethylenically unsaturated groups in one molecule.
  • the carboxy group-containing monomer may further have an acid group other than the carboxy group. Examples of acid groups other than carboxy groups include phenolic hydroxyl groups, phosphoric acid groups, and sulfonic acid groups.
  • the bifunctional or higher functional monomer having a carboxy group is not particularly limited, and can be appropriately selected from known compounds.
  • Examples of bifunctional or more functional monomers having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.), and Aronix M-510 (manufactured by Toagosei Co., Ltd.). manufactured by Toagosei Co., Ltd.) and the like.
  • bifunctional or higher functional monomers having a carboxy group examples include polymerizable compounds having a carboxy group described in paragraphs 0025 to 0030 of JP-A-2004-239942. The contents of this publication are incorporated herein.
  • Carboxy group-containing polymer- Carboxy group-containing polymers are usually alkali-soluble resins.
  • the definition and measurement method of alkali solubility are as described above.
  • the repeating units that the carboxy group-containing polymer can have are described below.
  • the carboxy group-containing polymer preferably has a repeating unit having a carboxy group.
  • Examples of repeating units having a carboxy group include repeating units represented by the following general formula (A).
  • R A1 represents a hydrogen atom, a halogen atom, or an alkyl group.
  • the above alkyl groups may be linear or branched.
  • the number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1.
  • a 1 represents a single bond or a divalent linking group.
  • divalent linking group examples include -CO-, -O-, -S-, -SO-, -SO 2 -, -NR N - (R N is a hydrogen atom or a alkyl groups), hydrocarbon groups (eg, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups such as phenylene groups, etc.), and linking groups in which a plurality of these are linked.
  • Examples of monomers from which repeating units having a carboxy group are derived include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid.
  • (meth)acrylic acid is preferable from the viewpoint of excellent patterning properties. That is, the repeating unit having a carboxy group is preferably a repeating unit derived from (meth)acrylic acid, and the polymer preferably contains a repeating unit derived from (meth)acrylic acid.
  • the carboxy group-containing polymer may contain a repeating unit having a carboxy group linked to the main chain by a linking group having 1 or more carbon atoms.
  • the linking group having 1 or more carbon atoms is not particularly limited, but an alkylene group, a cycloalkylene group, an arylene group, -CO-, -COO-, -OCO-, -NRCO-, and -NHCOO-, and their A combination is mentioned.
  • R above is a monovalent substituent.
  • the linking group may be a combination of the linking groups exemplified above and —O—, —S—, —NR—, —SO— and —SO 2 —.
  • R is a monovalent substituent.
  • the repeating unit having a carboxy group linked to the main chain by a linking group having 1 or more carbon atoms is preferably represented by the following formula (a1) or the following formula (a2).
  • R a represents a hydrogen atom or a monovalent substituent.
  • the monovalent substituent represented by R a includes a halogen atom and an alkyl group having 1 to 3 carbon atoms.
  • X represents a linking group having 1 or more carbon atoms.
  • the linking group represented by X includes the above linking groups having 1 or more carbon atoms, such as —CO—, —COO—, —NR NA — (where R NA is an alkyl group having 1 to 5 carbon atoms).
  • a connecting group X1 selected from a hydrocarbon group and a group combining these, and the connecting group X1 and -O-, -S-, -NH- and a group combining these and a linking group X2 formed from a linking group such as As the linking group having 1 or more carbon atoms, a linking group Y1 selected from an alkylene group, an arylene group, —COO—, an amide linking group, a carbonate linking group, a urethane linking group, a urea linking group and a group combining these, or , a linking group Y2 formed from the above linking group Y1 and a linking group selected from —O—, —S—, —NH— and groups in which these are combined is preferred, an alkylene group, a cycloalkylene group, an arylene group, -COO- or a group combining these is more preferred.
  • Y represents a cyclic structure.
  • the cyclic structure represented by Y may be an alicyclic ring or an aromatic ring, and each may be monocyclic or polycyclic.
  • the alicyclic ring preferably has 5 to 15 carbon atoms.
  • -CH 2 - constituting Y may be substituted with a divalent linking group.
  • the divalent linking groups include -CO-, -COO-, -OCO-, -NRCO-, -NHCOO-, -O-, -S-, -NR-, -SO- and -SO 2 - , as well as combinations thereof.
  • the number of carbon atoms in the aromatic ring is preferably 6-12.
  • the aromatic ring may be an aromatic ring containing elements other than carbon atoms.
  • Z represents a single bond or a linking group having 1 or more carbon atoms. At least one of Y and Z represents a group having 1 or more carbon atoms. Examples of the linking group having 1 or more carbon atoms represented by Z include the same linking groups as the linking groups represented by X above.
  • the carboxy group-containing polymer preferably has a repeating unit having a polymerizable group in addition to the repeating units described above.
  • the polymerizable group include ethylenically unsaturated groups (e.g., (meth)acryloyl group, allyl group, styryl group, etc.) and cyclic ether groups (e.g., epoxy group, oxetanyl group, etc.). preferably an ethylenically unsaturated group, more preferably an allyl group or a (meth)acryloyl group.
  • repeating units having a polymerizable group include repeating units represented by the following general formula (B).
  • X B1 and X B2 each independently represent -O- or -NR N -.
  • RN represents a hydrogen atom or an alkyl group.
  • the alkyl group may be linear or branched, and preferably has 1 to 5 carbon atoms.
  • L represents an alkylene group or an arylene group.
  • the alkylene group may be linear or branched, and preferably has 1 to 5 carbon atoms.
  • the arylene group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms.
  • the alkylene group and the arylene group may have a substituent, and the substituent is preferably an acid group, for example.
  • R B1 and R B2 each independently represent a hydrogen atom or an alkyl group.
  • the above alkyl groups may be linear or branched.
  • the number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1.
  • the repeating unit having a polymerizable group may be a repeating unit derived from a compound having an allyl group.
  • Examples of the above units include repeating units derived from allyl (meth)acrylate.
  • the content of repeating units having a polymerizable group in the carboxy group-containing polymer is preferably 3 to 60 mol%, more preferably 5 to 40 mol%, more preferably 10 to 30, based on the total repeating units of the carboxy group-containing polymer. Mole % is more preferred.
  • the carboxy group-containing polymer may have a repeating unit having specific structure S0 (preferably specific structure S1) in addition to the repeating units described above.
  • the specific structures S0 and S1 are as described above.
  • the specific structure S0 preferably the specific structure S1
  • the specific structure S0 may be present in the main chain, may be present in the side chain, or may be present in the side chain. preferably present in When the specific structure S0 (preferably the specific structure S1) is present in the side chain, the specific structure S0 (preferably the specific structure S1) is bound to the main chain of the polymer via a single bond or a linking group.
  • a repeating unit having a specific structure S0 is, for example, a monomer having a heteroaromatic ring (specifically, a vinyl heteroaromatic ring such as vinylpyridine and vinyl (iso)quinoline, and a heteroaromatic repeating units based on a (meth)acrylate monomer having a ring, etc.).
  • a monomer having a heteroaromatic ring specifically, a vinyl heteroaromatic ring such as vinylpyridine and vinyl (iso)quinoline, and a heteroaromatic repeating units based on a (meth)acrylate monomer having a ring, etc.
  • repeating unit having the specific structure S0 (preferably specific structure S1) are shown below, but are not limited thereto.
  • the content thereof is preferably 3 to 75 mol% with respect to the total repeating units of the carboxy group-containing polymer. ⁇ 60 mol% is more preferred, and 10 to 50 mol% is even more preferred.
  • the repeating unit having the specific structure S0 (preferably specific structure S1) may be used alone or in combination of two or more.
  • the carboxy group-containing polymer preferably has a repeating unit having an aromatic ring in addition to the above repeating units.
  • an aromatic hydrocarbon ring is preferable. Examples thereof include repeating units derived from (meth)acrylates having aromatic rings, and repeating units derived from styrene and polymerizable styrene derivatives.
  • (Meth)acrylates having an aromatic ring include, for example, benzyl (meth)acrylate, phenethyl (meth)acrylate and phenoxyethyl (meth)acrylate.
  • Styrene and polymerizable styrene derivatives include, for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimers and styrene trimers.
  • a repeating unit represented by formula (C) is also preferable.
  • R C1 represents a hydrogen atom, a halogen atom or an alkyl group.
  • the above alkyl groups may be linear or branched.
  • the number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1.
  • Ar C represents a phenyl group or a naphthyl group.
  • the phenyl group and the naphthyl group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aryl group, a halogen atom and a hydroxy group.
  • Ar 2 C is preferably a phenyl group.
  • repeating units having an aromatic ring examples include the following repeating units.
  • the content of repeating units having an aromatic ring in the carboxy group-containing polymer is preferably 5 to 80 mol%, more preferably 15 to 75 mol%, and 30 to 70 mol, based on the total repeating units of the carboxy group-containing polymer. % is more preferred.
  • the content of repeating units having an aromatic ring in the carboxy group-containing polymer is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and 30 to 70% by mass, based on the total repeating units of the carboxy group-containing polymer. % is more preferred.
  • the carboxy group-containing polymer preferably has a repeating unit having an alicyclic structure in addition to the repeating units described above.
  • Alicyclic structures may be monocyclic or polycyclic.
  • Alicyclic structures include, for example, dicyclopentanyl ring structures, dicyclopentenyl ring structures, isobornyl ring structures, adamantane ring structures, and cyclohexyl ring structures.
  • Monomers from which repeating units having an alicyclic structure are derived include, for example, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and cyclohexyl ( meth)acrylates.
  • the content of repeating units having an alicyclic structure in the carboxy group-containing polymer is preferably 3 to 70 mol%, more preferably 5 to 60 mol%, more preferably 10 to 55 mol % is more preferred.
  • the carboxy group-containing polymer may have other repeating units in addition to the repeating units described above.
  • Examples of monomers from which the other repeating units are derived include methyl (meth)acrylate.
  • the alkyl group in the (meth)acrylic acid alkyl ester includes, for example, an alkyl group.
  • the above alkyl group may be linear, branched or cyclic.
  • the above alkyl group may further have a substituent such as a hydroxy group.
  • the number of carbon atoms in the alkyl group is preferably 1-50, more preferably 1-10.
  • the content of other repeating units in the carboxy group-containing polymer is preferably 1 to 70 mol%, more preferably 2 to 50 mol%, and 3 to 20 mol%, based on the total repeating units of the carboxy group-containing polymer. More preferred.
  • the content of the carboxy group-containing polymer in compound A is preferably 75 to 100% by mass, more preferably 85 to 100% by mass, still more preferably 90 to 100% by mass, relative to the total mass of compound A. ⁇ 100% by weight is particularly preferred.
  • the content of the carboxy group-containing monomer in compound A is preferably 0 to 25% by mass, more preferably 0 to 10% by mass, and still more preferably 0 to 5% by mass, relative to the total mass of compound A.
  • the carboxy group-containing polymer may further have an acid group other than the carboxy group.
  • acid groups other than carboxy groups include phenolic hydroxyl groups, phosphoric acid groups, and sulfonic acid groups.
  • the lower limit of the weight-average molecular weight is preferably 5,000 or more, and 10,000 or more, in terms of excellent formability of the photosensitive layer (in other words, excellent film-forming ability for forming the photosensitive layer). More preferably, 11,000 is still more preferable, and 15,000 or more is particularly preferable.
  • the upper limit is not particularly limited, it is often 200,000 or less, and in terms of better adhesion (laminate adhesion) when laminating (transferring) to an arbitrary base material, 60,000 or less. It is preferable to have
  • the acid value of the carboxy group-containing polymer is preferably 60-300 mgKOH/g, more preferably 60-275 mgKOH/g, and even more preferably 75-250 mgKOH/g.
  • the acid value of the carboxy group-containing polymer is a value measured by the titration method specified in JIS K0070 (1992).
  • the lower limit of the content of compound A is preferably 1% by mass or more, more preferably 25% by mass or more, still more preferably 30% by mass or more, with respect to the total mass of the photosensitive layer. % by mass or more is even more preferred, and 50% by mass or more is particularly preferred.
  • the upper limit of the content of compound A is preferably 100% by mass or less, more preferably 99% by mass or less, still more preferably 97% by mass or less, and particularly 93% by mass or less, relative to the total mass of the photosensitive layer. It is preferably 85% by mass or less, more preferably 75% by mass or less, and most preferably 75% by mass or less.
  • the upper limit of the content of the compound A is preferably 99% by mass or less with respect to the total mass of the photosensitive layer.
  • the content of compound A is preferably 40 to 98% by mass, more preferably 50 to 96% by mass, based on the total mass of the photosensitive layer. , 60 to 93 mass % is more preferred.
  • the content of compound A is preferably 30 to 85% by weight, more preferably 45 to 75% by weight, based on the total weight of the photosensitive layer.
  • the content of compound A is preferably 30 to 85% by weight, more preferably 45 to 75% by weight, based on the total weight of the photosensitive layer.
  • the photosensitive layer preferably contains compound ⁇ .
  • Compound ⁇ is a compound having a structure (specific structure S0) that reduces the amount of carboxyl groups contained in compound A upon exposure. Note that the specific structure S0 is as described above.
  • the specific structure S0 of the compound ⁇ may be an entire structure that constitutes the entire compound ⁇ , or a partial structure that constitutes a part of the compound ⁇ .
  • the compound ⁇ may be a high-molecular compound or a low-molecular compound, preferably a low-molecular compound.
  • the molecular weight of compound ⁇ , which is a low-molecular compound is preferably less than 5,000, more preferably less than 1,000, even more preferably 65-300, and particularly preferably 75-250.
  • the compound ⁇ is preferably a compound B having a structure (specific structure S1) capable of accepting electrons from the carboxyl group contained in the compound A in a photoexcited state. According to compound B, it is believed that the carboxy group contained in compound A can be eliminated (decarboxylated) as CO2 .
  • the compound ⁇ (preferably the compound B) is preferably an aromatic compound because of its excellent pattern forming ability.
  • the aromatic compound is a compound having one or more aromatic rings. Only one aromatic ring or a plurality of aromatic rings may be present in compound ⁇ (preferably compound B). When a plurality of aromatic rings are present, for example, the aromatic ring may be present in a side chain of the resin or the like.
  • the aromatic ring can be used as a structure (specific structure S0 (preferably specific structure S1)) that reduces the amount of carboxy groups contained in compound A by exposure.
  • the aromatic ring may be monocyclic or polycyclic, and is preferably polycyclic.
  • the polycyclic aromatic ring is, for example, an aromatic ring formed by condensing a plurality of (for example, 2 to 5) aromatic ring structures, and at least one of the plurality of aromatic ring structures has a heteroatom as a ring member atom. It is preferable to have The aromatic ring may be a heteroaromatic ring, and preferably has one or more (eg, 1 to 4) heteroatoms (nitrogen atom, oxygen atom, sulfur atom, etc.) as ring member atoms. It is more preferable to have one or more (eg, 1 to 4) nitrogen atoms as .
  • the number of ring member atoms in the aromatic ring is preferably 5-15.
  • aromatic ring examples include monocyclic aromatic rings such as pyridine ring, pyrazine ring, pyrimidine ring, and triazine ring; Aromatic ring: aromatic ring in which three rings are condensed, such as acridine ring, phenanthridine ring, phenanthroline ring, and phenazine ring.
  • the aromatic ring may have one or more (for example, 1 to 5) substituents, and examples of the substituents include alkyl groups, aryl groups, halogen atoms, acyl groups, alkoxycarbonyl groups, arylcarbonyl groups, Carbamoyl groups, hydroxy groups, cyano groups, and nitro groups are included.
  • the aromatic ring has two or more substituents, the plurality of substituents may be combined to form a non-aromatic ring. It is also preferred that the aromatic ring is directly bonded to the carbonyl group to form an aromatic carbonyl group in compound ⁇ (preferably compound B). It is also preferred that multiple aromatic rings are linked via a carbonyl group.
  • the aromatic ring is bonded to the imide group to form an aromatic imide group in compound ⁇ (preferably compound B).
  • the imide group in the aromatic imide group may or may not form an imide ring together with the aromatic ring.
  • a plurality of aromatic rings e.g., 2 to 5 aromatic rings
  • the series of aromatic ring structures as a whole is regarded as one specific structure.
  • one or more of the plurality of aromatic rings constituting the series of aromatic ring structures is preferably the heteroaromatic ring.
  • Compound ⁇ (preferably compound B) is preferably a compound that satisfies one or more (eg, 1 to 4) of the following requirements (1) to (4) in terms of superior pattern forming ability. Above all, it is preferable that at least requirement (2) is satisfied, and that at least a nitrogen atom be included as the heteroatom possessed by the heteroaromatic ring. (1) It has a polycyclic aromatic ring. (2) having a heteroaromatic ring; (3) having an aromatic carbonyl group; (4) It has an aromatic imide group.
  • compound ⁇ examples include pyridine and pyridine derivatives, pyrazine and pyrazine derivatives, pyrimidine and pyrimidine derivatives, and monocyclic aromatic compounds such as triazine and triazine derivatives; quinoline and quinoline derivatives; Compounds in which two rings are fused to form an aromatic ring, such as isoquinoline and isoquinoline derivatives, quinoxaline and quinoxaline derivatives, and quinazoline and quinazoline derivatives; acridine and acridine derivatives, phenanthridine and phenanthridine derivatives, phenanthroline and Compounds in which three or more rings are condensed to form an aromatic ring, such as phenanthroline derivatives and phenazine and phenazine derivatives.
  • compound ⁇ (preferably compound B) is preferably one or more selected from the group consisting of pyridine and pyridine derivatives, quinoline and quinoline derivatives, and isoquinoline and isoquinoline derivatives. It is more preferably one or more selected from the group consisting of.
  • These compounds and derivatives thereof may further have a substituent, and examples of the substituent include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, A cyano group or a nitro group is preferred.
  • compound ⁇ when compound ⁇ (preferably compound B) is a polymer, it may be a polymer in which the specific structure is bound to the main chain of the polymer via a single bond or a linking group.
  • the compound ⁇ (preferably compound B), which is a polymer is, for example, a monomer having a heteroaromatic ring (specifically, a vinyl heteroaromatic ring and/or a specific structure (preferably a heteroaromatic ring) (meta ) acrylate monomer). You may copolymerize with another monomer as needed.
  • the absorption coefficient of compound ⁇ (preferably compound B) with respect to light having a wavelength of 365 nm is, for example, 10000 L/(mol cm) or less, and 1000 L/(mol cm) or less, in terms of superior pattern forming ability. is preferred, it is more preferably less than 500 L/(mol ⁇ cm), and even more preferably 100 L/(mol ⁇ cm) or less.
  • the lower limit of the absorption coefficient is not particularly limited, and is, for example, over 0 L/(mol ⁇ cm).
  • the absorption coefficient for light with a wavelength of 365 nm is the absorption coefficient measured by dissolving compound ⁇ (preferably compound B) in acetonitrile.
  • the solvent for dissolving compound ⁇ may be changed as appropriate.
  • the fact that the absorption coefficient of compound ⁇ (preferably compound B) is within the above range is particularly advantageous when the photosensitive layer is exposed through a temporary support (preferably PET film). That is, since the absorption coefficient is moderately low, generation of bubbles due to decarboxylation can be controlled even when exposed through the temporary support, and deterioration of the pattern shape can be prevented.
  • the compound having such an absorption coefficient is preferably the above-mentioned monocyclic aromatic compound or an aromatic compound in which two rings are condensed to form an aromatic ring, and pyridine or a pyridine derivative, quinoline or a quinoline derivative, Alternatively, isoquinoline or isoquinoline derivatives (iso)quinoline derivatives are preferred.
  • compound ⁇ (preferably compound B) include 5,6,7,8-tetrahydroquinoline, 4-acetylpyridine, 4-benzoylpyridine, isoquinoline, 1-methylisoquinoline, 1-phenylisoquinoline, quinoline, and acridine. , and phenanthridine.
  • the content of the compound ⁇ (preferably compound B) in the photosensitive layer is preferably 0.1 to 50% by weight based on the total weight of the photosensitive layer in terms of better pattern forming ability.
  • the content of compound ⁇ (preferably compound B) is preferably 2.0 to 40% by mass with respect to the total weight of the photosensitive layer, 4 to 35% by mass is more preferable, and 8 to 30% by mass is even more preferable.
  • the content of compound ⁇ (preferably compound B) is preferably 0.5 to 20% by mass, and preferably 1.0% by mass, based on the total mass of the photosensitive layer. ⁇ 10% by mass is more preferred.
  • the content of compound ⁇ is preferably 0.3 to 20% by mass, preferably 0.5% by mass, based on the total mass of the photosensitive layer. ⁇ 8% by mass is more preferred.
  • Compound ⁇ (preferably compound B) may be used singly or in combination of two or more.
  • the total number of (specific structure S0 (preferably specific structure S1)) possessed by compound ⁇ (preferably compound B) in the photosensitive layer is the total number of carboxy groups possessed by compound A in terms of superior pattern forming ability. is preferably 1 mol % or more, more preferably 3 mol % or more, still more preferably 5 mol % or more, and particularly preferably 10 mol % or more.
  • the upper limit of the total number of (specific structure S0 (preferably specific structure S1)) possessed by compound ⁇ (preferably compound B) is not particularly limited, but from the viewpoint of the film quality of the resulting film, the carboxy group possessed by compound A ( preferably 200 mol % or less, more preferably 100 mol % or less, and even more preferably 80 mol % or less, relative to the total number of carboxyl groups).
  • the photosensitive layer may contain a polymerizable compound.
  • This polymerizable compound is a component different from the compound A having a carboxy group and does not contain a carboxy group.
  • the polymerizable compound is preferably a component different from compound A.
  • it is preferably a compound having a molecular weight (weight average molecular weight if it has a molecular weight distribution) of less than 5,000, and is a polymerizable monomer. is also preferred.
  • a polymerizable compound is a polymerizable compound having one or more (eg, 1 to 15) ethylenically unsaturated groups in one molecule.
  • the polymerizable compound preferably contains a polymerizable compound having a functionality of two or more.
  • the bifunctional or higher polymerizable compound means a polymerizable compound having two or more (for example, 2 to 15) ethylenically unsaturated groups in one molecule.
  • Examples of ethylenically unsaturated groups include (meth)acryloyl groups, vinyl groups, and styryl groups, with (meth)acryloyl groups being preferred.
  • (Meth)acrylates are preferred as the polymerizable compound.
  • the photosensitive layer preferably contains a bifunctional polymerizable compound (preferably a difunctional (meth)acrylate) and a trifunctional or higher polymerizable compound (preferably a trifunctional or higher (meth)acrylate). .
  • the bifunctional polymerizable compound is not particularly limited and can be appropriately selected from known compounds.
  • Examples of bifunctional polymerizable compounds include tricyclodecanedimethanol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6 - hexanediol di(meth)acrylates.
  • the bifunctional polymerizable compound includes, for example, tricyclodecanedimethanol diacrylate (manufactured by A-DCP Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP Shin-Nakamura Kagaku Kogyo Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (A-HD-N Shin-Nakamura Chemical Kogyo Co., Ltd.) and the like.
  • tricyclodecanedimethanol diacrylate manufactured by A-DCP Shin-Nakamura Chemical Co., Ltd.
  • tricyclodecanedimethanol dimethacrylate DCP Shin-Nakamura Kagaku Kogyo Co., Ltd.
  • 1,9-nonanediol diacrylate A-NOD-N Shin-N
  • the trifunctional or higher polymerizable compound is not particularly limited and can be appropriately selected from known compounds.
  • Examples of trifunctional or higher polymerizable compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth)acrylate, pentaerythritol (tri/tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, Examples include ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds 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.
  • polymerizable compounds include, for example, 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 compounds of (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) manufactured by Daicel Allnex ) 135, etc.), and ethoxylated glycerin triacrylate (A-GLY-9E, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.
  • (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) manufactured by Daicel Allnex ) 135, etc.
  • A-GLY-9E ethoxylated glycerin triacrylate
  • Examples of polymerizable compounds include urethane (meth)acrylates (preferably trifunctional or higher urethane (meth)acrylates).
  • the lower limit of the number of functional groups is preferably 6 or more, more preferably 8 or more.
  • the upper limit of the number of functional groups is preferably 20 or less.
  • Trifunctional or higher urethane (meth)acrylates include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.); UA-32P, U-15HA and UA-1100H (all manufactured by Shin-Nakamura Chemical Co., Ltd.); Kyoeisha Chemical Co., Ltd. AH-600; UA-306H, UA-306T, UA-306I, UA-510H and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.).
  • the molecular weight of the polymerizable compound (the weight average molecular weight when it has a molecular weight distribution) is preferably less than 5,000, more preferably 200-3000, still more preferably 250-2600, and particularly preferably 280-2200.
  • the minimum molecular weight is preferably 250 or more, more preferably 280 or more.
  • the content of the polymerizable compound is preferably 3 to 70% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 55% by mass, based on the total solid content of the photosensitive composition.
  • the content of the bifunctional polymerizable compound is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, based on the total mass of all polymerizable compounds contained in the photosensitive composition, and 30 to 80% by mass. % by mass is more preferred.
  • the content of the trifunctional or higher polymerizable compound is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, based on the total mass of all polymerizable compounds contained in the photosensitive composition. 20 to 70% by mass is more preferable.
  • the photosensitive composition may contain a bifunctional or higher functional polymerizable compound and a monofunctional polymerizable compound.
  • the polymerizable compound contained in the photosensitive composition is mainly composed of a polymerizable compound having a functionality of 2 or more.
  • the content of the bifunctional or higher polymerizable compound is preferably 60 to 100% by mass, preferably 80 to 100% by mass, based on the total mass of all polymerizable compounds contained in the photosensitive composition. More preferably, 90 to 100% by mass is even more preferable.
  • the photosensitive layer does not substantially contain a polymerizable compound from the viewpoint of better color visibility.
  • substantially free of polymerizable compound means that the content of the polymerizable compound may be less than 3% by mass, with respect to the total mass of the photosensitive layer, and may be 0 to 1% by mass. It is preferably 0 to 0.1% by mass, and more preferably 0 to 0.1% by mass.
  • the photosensitive layer may contain a photopolymerization initiator.
  • the photopolymerization initiator may be a radical photopolymerization initiator, a cationic photopolymerization initiator, or an anionic photopolymerization initiator, and is preferably a radical photopolymerization initiator.
  • the photopolymerization initiator is preferably at least one selected from the group consisting of oxime ester compounds (photopolymerization initiators having an oxime ester structure) and aminoacetophenone compounds (photopolymerization initiators having an aminoacetophenone structure). , more preferably includes compounds of both. When both of these compounds are included, the content of the oxime ester compound is preferably 5-90% by mass, more preferably 15-50% by mass, based on the total content of both compounds.
  • Other photopolymerization initiators may be included in addition to the above photopolymerization initiators.
  • Other photopolymerization initiators include, for example, hydroxyacetophenone compounds, acylphosphine oxide compounds and bistriphenylimidazole compounds.
  • photopolymerization initiators also include polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-095716 and paragraphs 0064-0081 of JP-A-2015-014783.
  • oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)] (trade name: IRGACURE OXE-01, IRGACURE series, manufactured by BASF ), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF) ), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazoyl][2-(2,2,3,3-tetrafluoropropoxy ) Phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)
  • aminoacetophenone compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, The Omnirad series is a product of IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907), APi-307 (1-( biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).
  • photopolymerization initiators include, for example, 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl ⁇ -2-methyl-propan-1-one ( Product name: Omnirad 127), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (product name: Omnirad 369), 2-hydroxy-2-methyl-1-phenyl-propane -1-one (trade name: Omnirad 1173), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Omnirad 184), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad) 651), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819). .
  • a photoinitiator may be used individually by 1 type or in 2 or more types.
  • the content thereof is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, more preferably 0.5 to 10% by mass, based on the total mass of the photosensitive layer. 5% by mass is more preferred.
  • the photosensitive layer does not substantially contain a photopolymerization initiator.
  • substantially free of photopolymerization initiator means that the content of the photopolymerization initiator may be less than 0.1% by mass with respect to the total weight of the photosensitive layer, and 0 to 0.05 % by mass is preferable, and 0 to 0.01% by mass is more preferable.
  • the photosensitive layer may contain a surfactant.
  • Surfactants include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, with nonionic surfactants being preferred.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. mentioned.
  • surfactants described in paragraphs 0120 to 0125 of WO 2018/179640 can also be used.
  • surfactant the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362 can also be used.
  • fluorosurfactants include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, and F-144.
  • an acrylic compound that has a molecular structure with a functional group containing a fluorine atom and in which the portion of the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied can also be suitably used.
  • fluorine-based surfactants include Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafac and DS-21.
  • the fluorosurfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
  • a block polymer can also be used as the fluorosurfactant.
  • the fluorine-based surfactant has a structural unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups).
  • a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound can also be preferably used.
  • a fluoropolymer having an ethylenically unsaturated bond-containing group in a side chain can also be used.
  • Megafac RS-101, RS-102, RS-718K, RS-72-K manufactured by DIC Corporation
  • DIC Corporation Megafac RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation) and the like.
  • fluorine-based surfactants from the viewpoint of improving environmental friendliness, compounds having linear perfluoroalkyl groups having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are used.
  • PFOA perfluorooctanoic acid
  • PFOS perfluorooctane sulfonic acid
  • Surfactants derived from alternative materials are preferred.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2 , 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NC
  • silicone-based surfactants include straight-chain polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains and terminals.
  • surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (Toray Dow Corning Co., Ltd.), X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643 , X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101KP-103, KP-104, KP-105, KP-106, KP-109 , KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-120
  • Surfactants may be used singly or in combination of two or more.
  • the content of the surfactant is preferably 0.0001 to 10% by mass, more preferably 0.001 to 5% by mass, still more preferably 0.005 to 3% by mass, based on the total mass of the photosensitive layer.
  • the photosensitive layer may contain other additives as needed.
  • Other additives include, for example, plasticizers, sensitizers, heterocyclic compounds, alkoxysilane compounds, and the like.
  • Plasticizers, sensitizers, heterocyclic compounds, and alkoxysilane compounds include, for example, those described in paragraphs 0097 to 0119 of WO 2018/179640.
  • the solvent may remain, but the solvent may not be contained in the photosensitive layer.
  • the content of the solvent in the photosensitive layer is preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and particularly 0.5% by mass or less, relative to the total mass of the photosensitive layer.
  • 0.1% by mass or less is most preferable.
  • the lower limit is not particularly limited, it may be 0% by mass.
  • the photosensitive layer contains other additives such as rust inhibitors, metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, Known additives such as thermal acid generators, UV absorbers, thickeners, cross-linking agents, and organic or inorganic suspending agents may also be included. Preferred aspects of these components are described in paragraphs 0165 to 0184 of JP-A-2014-085643, respectively, and the contents of this publication are incorporated herein.
  • the photosensitive layer may contain impurities.
  • Impurities include, for example, sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof.
  • halide ions, sodium ions, and potassium ions tend to be mixed as impurities, so the following contents are particularly preferable.
  • the content of impurities in the photosensitive layer is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, relative to the total mass of the photosensitive layer.
  • the content of impurities in the photosensitive layer may be 1 mass ppb or more, or 0.1 mass ppm or more with respect to the total mass of the photosensitive layer.
  • the impurities within the above range, for example, a raw material for the photosensitive component with a low impurity content is selected, the impurities are prevented from being mixed during the formation of the photosensitive layer, and the impurities are removed by washing. to do.
  • the amount of impurities can be made within the above range.
  • Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.
  • ICP Inductively Coupled Plasma
  • the content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer is small. is preferred.
  • the content of these compounds in the photosensitive layer is preferably 100 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 4 ppm by mass or less, relative to the total mass of the photosensitive layer.
  • the lower limit of the content may be 10 mass ppb or more or 100 mass ppb or more with respect to the total mass of the photosensitive layer.
  • the content of these compounds can be suppressed in the same manner as the metal impurities described above. Moreover, it can quantify by a well-known measuring method.
  • the content of water in the photosensitive layer is preferably 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, based on the total mass of the photosensitive layer, from the viewpoint of improving patterning properties. more preferred.
  • the average thickness of the photosensitive layer is preferably 0.5-20 ⁇ m. When the average thickness of the photosensitive layer is 20 ⁇ m or less, the pattern resolution is more excellent, and when the average thickness of the photosensitive layer is 2.0 ⁇ m or more, it is preferable from the viewpoint of color visibility.
  • the average thickness of the photosensitive layer is more preferably 0.8 to 15 ⁇ m, still more preferably 1.0 to 10 ⁇ m. Specific examples of the average thickness of the photosensitive layer include 3.0 ⁇ m, 4.0 ⁇ m, and 8.0 ⁇ m.
  • a colored layer is a layer containing a coloring agent.
  • the colored layer preferably contains at least one of a polymer and a monomer, more preferably a polymer and a monomer, in addition to the colorant.
  • the components of the colored layer are described below.
  • Colorants contained in the colored layer are not particularly limited, and known ones can be used.
  • the colorant may be either a dye or a pigment, preferably a pigment.
  • a dye refers to a substance that dissolves in a solvent
  • a pigment refers to a substance that does not dissolve in a solvent. Therefore, even those listed as dyes below may correspond to pigments depending on the solvent. Further, even the pigments listed below may correspond to dyes depending on the solvent.
  • the dye may be either an inorganic dye or an organic dye, and examples thereof include squarylium-based, pyrazoleazo-based, anilinoazo-based, triarylmethane-based, anthraquinone-based, anthrapyridone-based, benzylidene-based, oxonol-based, and pyrazolotriazole-based dyes. Examples include azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, and pyrromethene dyes. Multimers of these dyes may also be used. In addition, the dyes described in JP-A-2015-028144 and JP-A-2015-034966 can also be used.
  • the pigment may be either an inorganic pigment or an organic pigment, and examples thereof include black pigments, white pigments, and chromatic pigments other than black and white.
  • black pigments include carbon black, carbon nanotubes, titanium oxide, titanium carbide, iron oxide, composite oxides of copper and chromium, titanium oxide, titanium nitride, and graphite. Nanotubes are preferred.
  • white pigments include titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate, with titanium oxide or zinc oxide being preferred.
  • chromatic pigments examples include phthalocyanine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo, disazo, polyazo, etc. Examples include azo pigments.
  • chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter CI) 42595), Auramine (CI 41000), Fat Black HB (CI 26150), Mono Light Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB ( CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Spra (CI Pigment Red 11) Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. Pigment Black 1) and Carbon, C.I. I.
  • Pigment Red 97 C.I. I. Pigment Red 122, C.I. I. Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64, and C.I. I. Pigment Violet 23 and the like.
  • the number average particle size is preferably 0.001 to 0.1 ⁇ m, more preferably 0.01 to 0.08 ⁇ m, from the viewpoint of dispersibility in the colored layer.
  • the particle size refers to the diameter of a circle obtained by obtaining the area of a pigment particle from an image of the pigment particle taken with an electron microscope and considering a circle having the same area as the area of the pigment particle. , is an average value obtained by obtaining the above-mentioned particle diameters for 100 arbitrary particles and arithmetically averaging the obtained 100 particle diameters.
  • the particle size of the pigment can be adjusted by a known method.
  • colorant may be used alone, or two or more types may be used. Also, dyes and pigments may be used in combination.
  • the content of the coloring agent in the colored layer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total mass of the colored layer.
  • the total content of the colorants is preferably within the above range.
  • polymer examples of the polymer that the colored layer preferably contains include the above carboxy group-containing polymers. However, it is preferable not to include the above specific structure. Since the rest is the same as the carboxyl group-containing polymer, description thereof is omitted.
  • the content of the polymer in the colored layer is preferably 15 to 90% by mass, more preferably 30 to 80% by mass, based on the total mass of the colored layer.
  • Monomers that are preferably contained in the colored layer include a polymerizable compound that may be contained in the photosensitive layer and a carboxyl group-containing monomer, and description of each compound is omitted.
  • the content of the monomer in the colored layer is preferably 5 to 80% by mass, more preferably 15 to 60% by mass, based on the total mass of the colored layer.
  • the colored layer may contain a photopolymerization initiator.
  • the photopolymerization initiator include photopolymerization initiators that may be contained in the photosensitive layer, and are the same as the photopolymerization initiators described above, so description thereof is omitted.
  • the content of the photopolymerization initiator in the colored layer is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, based on the total mass of the colored layer. Especially preferred.
  • the colored layer may contain a surfactant.
  • surfactants include surfactants that may be contained in the photosensitive layer, and are the same as the surfactants described above, so description thereof is omitted.
  • the content of the surfactant in the colored layer is preferably 0.0001 to 10% by mass, more preferably 0.001 to 5% by mass, and 0.005 to 3% by mass with respect to the total mass of the colored layer. is more preferred.
  • Additives that may be contained in the colored layer include additives that may be contained in the above-described photosensitive layer, and are the same as the above-described additives, so description thereof will be omitted.
  • the colored layer preferably includes a dispersant and a dispersing aid as additives.
  • optical density of the colored layer at a wavelength of 550 nm is preferably 1.0 or more.
  • the optical density is more preferably 1.5 or higher, and even more preferably 2.0 or higher.
  • the upper limit of the optical density is not particularly limited, it is preferably 5.0 or less, more preferably 4.0 or less, from the viewpoints of light absorption and reflectance reduction of the colored layer and curability.
  • the thickness of the colored layer may be adjusted depending on the application of the transfer film, and is not particularly limited.
  • the thickness of the colored layer is preferably 2 to 50 ⁇ m, more preferably 5 to 30 ⁇ m, from the viewpoints of light absorption, reflectance reduction, and curability of the colored layer.
  • the ratio of the thickness of the photosensitive layer to the thickness of the colored layer is preferably 0.1 to 5.0, more preferably 0.1 to 1.0.
  • the transfer film of the present invention may have a cover film on the surface of the colored layer opposite to the photosensitive layer side.
  • the number of fisheyes having a diameter of 80 ⁇ m or more contained in the cover film is preferably 5/m 2 or less.
  • fish eye refers to material foreign matter, undissolved matter, and/or Alternatively, an oxidative degradation product or the like is taken into the film.
  • the number of particles having a diameter of 3 ⁇ m or more contained in the cover film is preferably 30 particles/mm 2 or less, more preferably 10 particles/mm 2 or less, and even more preferably 5 particles/mm 2 or less. Thereby, it is possible to suppress the defects caused by the unevenness caused by the particles contained in the cover film being transferred to the photosensitive layer.
  • the arithmetic mean roughness Ra of the surface of the cover film is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and even more preferably 0.03 ⁇ m or more. If Ra is within such a range, for example, when the transfer film is elongated, it is possible to improve the take-up property when the transfer film is taken up. From the viewpoint of suppressing defects during transfer, Ra is preferably less than 0.50 ⁇ m, more preferably 0.40 ⁇ m or less, and even more preferably 0.30 ⁇ m or less.
  • Cover films include, for example, polyethylene terephthalate films, polypropylene films, polystyrene films, and polycarbonate films.
  • cover film for example, those described in paragraphs 0083 to 0087 and 0093 of JP-A-2006-259138 may be used.
  • Alphan (registered trademark) FG-201 manufactured by Oji F-Tex Co., Ltd. Alphan (registered trademark) E-201F manufactured by Oji F-Tex Co., Ltd., Toray Advanced Film Co., Ltd.
  • Therapeal (registered trademark) 25WZ manufactured by Toray Industries, Inc. or Lumirror (registered trademark) 16QS62 (16KS40) manufactured by Toray Industries, Inc. may also be used.
  • the transfer film may include layers other than the layers described above (hereinafter also referred to as "other layers").
  • Other layers include, for example, an intermediate layer, a thermoplastic resin layer, a high refractive index layer, and the like, and known layers can be appropriately employed.
  • thermoplastic resin layer Preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP-A-2014-085643, and preferred embodiments of layers other than the above are described in paragraphs 0194-0196 of JP-A-2014-085643. Yes, the contents of this publication are incorporated herein.
  • the production method of the transfer film is not particularly limited, and known production methods can be applied.
  • Examples of the method for producing the transfer film include a method in which a photosensitive layer is formed on a temporary support by the following forming method, and then a colored layer is formed on the photosensitive layer by the following method. Furthermore, after forming the colored layer, the surface of the colored layer and the cover film may be pasted together. Further, after the step of forming the photosensitive layer, a high refractive index layer may be formed by further coating and drying a composition for forming a high refractive index layer containing the components of the high refractive index layer. .
  • the transfer film manufacturing method is a method of laminating a photosensitive layer formed on a temporary support and a colored layer formed on the temporary support so that the photosensitive layer and the colored layer face each other.
  • the temporary support for the colored layer may not be peeled after the production of the transfer film, but may serve as a cover film for the produced transfer film.
  • the method for forming the photosensitive layer and the colored layer will be described below.
  • a method for forming the photosensitive layer is not particularly limited, and a known method can be applied.
  • a method for forming the photosensitive layer a method including the step of forming a photosensitive layer by coating and drying a coating liquid containing a solvent and components contained in the photosensitive layer on a temporary support is preferred. .
  • a method for forming the colored layer is not particularly limited, and a known method can be applied.
  • the method for forming the colored layer includes a step of forming a colored layer by applying and drying a coating solution containing a solvent and components contained in the colored layer on the temporary support or the photosensitive layer.
  • a method comprising: When a pigment is used as the colorant, it is preferable to use a pigment dispersion when preparing a coating liquid for forming a colored layer.
  • the dispersion liquid may be prepared by adding a mixture obtained by previously mixing a pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing the mixture with a dispersing machine.
  • the pigment dispersant may be selected according to the pigment and solvent, and commercially available dispersants can be used, for example.
  • the vehicle refers to the part of the medium in which the pigment is dispersed in the case of a pigment dispersion liquid, and is a liquid binder component that holds the pigment in a dispersed state and a solvent component that dissolves and dilutes the binder component ( organic solvents) and
  • the disperser is not particularly limited, and includes known dispersers such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Furthermore, it may be finely pulverized using frictional force by mechanical grinding. Regarding the dispersing machine and the fine pulverization, reference can be made to the description in "Encyclopedia of Pigment” (Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).
  • the photosensitive layer is preferably the photosensitive layer of Embodiment X-1-a1 or Embodiment X-1-a2.
  • the photosensitive layer is preferably the photosensitive layer of Embodiment X-1-a1.
  • the laminate manufacturing method is preferably applied to a transfer film including the photosensitive layer of Embodiment X-1-a1 or Embodiment X-1-a2 described above. Each step of the preferred method for producing a laminate will be described in detail below.
  • the bonding step is a step of bonding the transfer film and the substrate by bringing the surface of the transfer film opposite to the temporary support into contact with the surface of the substrate.
  • the lamination step is preferably a lamination step by pressing and heating with rolls or the like.
  • a known laminator such as a laminator, a vacuum laminator, and an autocut laminator can be used for bonding.
  • the bonding process may be performed by a roll-to-roll method. The roll-to-roll method will be described below.
  • the roll-to-roll method uses a base material that can be wound and unwound as a base material, and the step of unwinding the base material (also referred to as an “unwinding step”), and after any of the steps, a step of winding the substrate (also referred to as a “winding step”), and at least one of the steps is performed to transport the substrate. It is a method to do while doing.
  • the unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and known methods may be used in manufacturing methods to which a roll-to-roll system is applied.
  • the substrate used in the lamination step is not particularly limited.
  • the shape of the substrate is not particularly limited, and may be plate-like, tube-like, fibrous, spherical, and the like. Moreover, the surface of the substrate may be flat, concave, or convex.
  • Materials constituting the base material are not particularly limited, and known materials can be used. Materials constituting the base material include, for example, metals, semiconductors, glass, ceramics, and resins.
  • the exposure step is a step of patternwise exposing the photosensitive layer.
  • the photosensitive layer of the transfer film of the present invention is exposed to light, the content of carboxyl groups derived from compound A in the photosensitive layer decreases. More specifically, using light having a wavelength that excites a specific structure (in the case of requirement V1) in compound ⁇ (preferably compound B) and a specific structure in compound A (in the case of requirement W1) in the photosensitive layer It is preferable to subject the photosensitive layer to pattern exposure.
  • the colored layer may be sensitized by exposure with which the photosensitive layer is irradiated.
  • a step of exposing the colored layer may be performed separately from the exposure of the photosensitive layer.
  • the colored layer may be subjected to pattern exposure using exposure light to which only the colored layer is exposed, followed by pattern exposure using exposure light to which only the photosensitive layer is exposed.
  • the step of exposing the colored layer is performed separately from the exposure of the photosensitive layer, the colored layer may be exposed in a pattern different from that of the photosensitive layer.
  • the light source used for exposure light in a wavelength range capable of reducing the content of carboxyl groups derived from compound A in the photosensitive layer (compound ⁇ in the photosensitive layer (preferably compound B)
  • Light having a wavelength that excites the specific structure (for requirement V1) and the specific structure in compound A (for requirement W1) is preferred.
  • the photosensitive layer is the photosensitive layer described above
  • light in wavelength ranges such as 254 nm, 313 nm, 365 nm, and 405 nm can be used.
  • ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, LEDs (Light Emitting Diodes), and the like are included.
  • the reaction in the colored layer is preferably excited by the exposure light used for exposing the photosensitive layer.
  • the colored layer and the photosensitive layer are separately exposed, the colored layer may be exposed with the exposure light to which only the photosensitive layer is exposed, and then the photosensitive layer may be exposed to the exposure light to which only the photosensitive layer is exposed. After exposure to light, at least the colored layer may be exposed to light.
  • the exposure amount is preferably 10-10000 mJ/cm 2 , more preferably 50-3000 mJ/cm 2 .
  • the pattern exposure may be exposure through a mask or direct exposure using a laser or the like. Also, the detailed arrangement and specific size of the pattern are not particularly limited. Exposure through a mask is preferable in terms of easy formation of the pattern described above, and exposure through a mask having openings corresponding to the arrangement of the protrusions is more preferable.
  • the shape of one opening is not particularly limited, and may be polygonal or circular. Polygons include triangles, quadrilaterals, pentagons, hexagons, and the like.
  • the mask pattern is preferably a mask having openings corresponding to the arrangement of the protrusions. Examples of the mask pattern include a mask pattern in which openings are arranged in a square lattice. It doesn't have to be.
  • the above mask pattern can be suitably applied when the developer in the subsequent development step is an alkaline developer.
  • the developing solution used in the subsequent development step is an organic solvent, it is preferable to use a mask pattern in which the openings and mask portions of the mask pattern are reversed.
  • pattern exposure may be performed after peeling the temporary support from the photosensitive layer, and before peeling the temporary support, pattern exposure is performed through the temporary support, and then the temporary support is peeled off.
  • the peeling step is a step of peeling off the temporary support between the bonding step and the exposure step, or between the exposure step and the development step described below.
  • a method for peeling the temporary support from the photosensitive layer is not particularly limited, and a known method is employed.
  • the developing step is a step of developing the exposed photosensitive layer using a developer to form a laminate including a pattern of a plurality of protrusions.
  • the difference in solubility in the developer (dissolution contrast) between the exposed area and the unexposed area is due to the decrease in the content of carboxyl groups in the photosensitive layer in the exposed area. is occurring.
  • the formation of a dissolution contrast in the photosensitive layer enables pattern formation in the development process.
  • the colored layer has photosensitivity and is exposed to light in the above-described exposure step, the colored layer has a dissolution contrast between the exposed portion and the unexposed portion, and the colored layer in the development step.
  • the positions of the unexposed area and the exposed area of the photosensitive layer may or may not correspond to the positions of the unexposed area and the exposed area of the colored layer.
  • the colored layer does not have photosensitivity, it is preferable that the colored layer does not dissolve in the developer.
  • the developer in the developing step is an alkaline developer
  • the developing step removes the unexposed portion to form a negative pattern.
  • the developer in the developing step is an organic solvent-based developer
  • the exposed portion is removed by performing the developing step to form a positive pattern.
  • the obtained positive pattern may be subjected to a treatment for reducing the content of carboxyl groups derived from compound A by a post-exposure step described later.
  • the alkaline developer is not particularly limited as long as it can remove the unexposed portion of the photosensitive layer.
  • an aqueous alkaline developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol/L (liter) is preferable.
  • the alkaline developer may further contain a water-soluble organic solvent, a surfactant, and the like.
  • the alkaline developer for example, the developer described in paragraph 0194 of International Publication No. 2015/093271 is preferable.
  • Organic solvent-based developer is not particularly limited as long as it can remove the exposed portion of the photosensitive layer. Examples include ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbons.
  • a developer containing an organic solvent such as a system solvent can be used.
  • a plurality of organic solvents may be mixed, or an organic solvent other than the above or water may be mixed and used.
  • the water content of the organic solvent-based developer as a whole is preferably less than 10% by mass, and more preferably substantially free of water.
  • the concentration of the organic solvent (in the case of multiple mixtures, the total) in the organic solvent-based developer is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 85% by mass or more, and particularly preferably 90% by mass or more. , 95 mass % or more is most preferable. In addition, as an upper limit, it is 100 mass % or less, for example.
  • the development method is not particularly limited, and may be any of puddle development, shower development, spin development, dip development, and the like.
  • shower development will be described. Unnecessary portions can be removed by spraying a developer onto the exposed photosensitive layer by showering. Further, after development, a cleaning agent or the like may be sprayed with a shower, and development residues may be removed while rubbing with a brush or the like.
  • the liquid temperature of the developer is preferably 20 to 40.degree.
  • Post-baking process and post-exposure process After the development step, a post-baking step of heat-treating the pattern obtained by development and/or a post-exposure step of further exposing the pattern obtained by development may be included.
  • the post-baking process is preferably performed under an environment of 8.1 to 121.6 kPa, more preferably under an environment of 50.66 kPa or more.
  • the post-baking step is more preferably performed under an environment of 111.46 kPa or less, and even more preferably under an environment of 101.3 kPa or less.
  • the temperature of the post-baking step is preferably 80 to 250°C, more preferably 110 to 170°C, even more preferably 130 to 150°C.
  • the post-baking process time is preferably 1 to 60 minutes, more preferably 2 to 50 minutes, even more preferably 5 to 40 minutes.
  • the post-baking process may be performed in an air environment or in a nitrogen-substituted environment.
  • the post-exposure step it is preferable to expose a pattern obtained by developing without using a mask.
  • the light source used for exposure is preferably the light source described in the exposure step.
  • the exposure amount is preferably 10-10000 mJ/cm 2 , more preferably 50-3000 mJ/cm 2 .
  • the developer in the development step is an organic solvent-based developer, it is preferable to subject the obtained positive pattern to a post-exposure step.
  • the exposure can reduce the content of carboxyl groups derived from compound A. More specifically, light having a wavelength that excites the specific structure (in the case of requirement V1) in compound ⁇ (preferably compound B) and the specific structure in compound A (in the case of requirement W1) in the photosensitive layer is used. It is preferable to expose a positive pattern.
  • the specific structure in compound ⁇ (preferably compound B) (in the case of requirement V1) and a first exposure step of exposing with light having a wavelength that excites the specific structure (in the case of requirement W1) in compound A, and causing a reaction of the polymerizable compound based on the photopolymerization initiator in the photosensitive layer and a second exposure step of exposing with light in a wavelength range that allows
  • the wavelength of the light used in the first exposure step can be appropriately selected as long as the specific structure can be excited.
  • the light source that emits the light can be appropriately selected.
  • the exposure amount in the first exposure step is preferably 10-10000 mJ/cm 2 , more preferably 50-3000 mJ/cm 2 .
  • the wavelength of the light used in the second exposure step can be appropriately selected as long as it is possible to cause the reaction of the polymerizable compound based on the photopolymerization initiator.
  • the light source that emits the light can be appropriately selected.
  • the exposure amount in the second exposure step is preferably 5-200 mJ/cm 2 , more preferably 10-150 mJ/cm 2 .
  • FIG. 2 is a schematic top view showing an example of a laminate
  • FIG. 3 is a schematic side view thereof.
  • An example of the laminate is formed by the colored layer being photosensitive, the entire colored layer being exposed to the exposure light irradiated to the photosensitive layer, the colored layer remaining, and a part of the photosensitive layer being removed by development. It is a laminated body.
  • a method of performing processing such that only the photosensitive layer is developed, a method of exposing the colored layer and the photosensitive layer with different wavelengths and masks
  • the laminate can be formed by using various methods such as a method using a non-photosensitive colored layer.
  • the laminate 20 includes a substrate 22 , a colored layer 24 , and a pattern 28 made up of a plurality of protrusions 26 arranged on the colored layer 24 .
  • the pattern 28 made up of the protrusions 26 functions as a so-called moth-eye structure to suppress reflection of light incident from the pattern 28 side of the laminate 20 .
  • the plurality of protrusions 26 have a tapered shape in which the width increases from one end on the side opposite to the base material 22 toward the other end on the side of the base material 22 . Therefore, the refractive index continuously increases from the pattern 28 of the laminate 20 toward the substrate 22 side.
  • the pattern 28 functions as a moth-eye structure and suppresses light reflection. Therefore, the color derived from the coloring agent contained in the colored layer 24 can be easily visually recognized, and the color visibility is excellent.
  • FIGS. 2 and 3 show an example in which the protrusions 26 are arranged in a square lattice
  • the regularity of the arrangement is not particularly limited, and the regularity may be, for example, a checkered pattern or a triangular lattice. , and hexagonal lattices. Moreover, it does not have to have regularity.
  • As a method for forming a state in which the protrusions 26 are arranged in a square lattice pattern as described above there is a method of exposing and developing the photosensitive layer using a mask having openings arranged in a square lattice pattern. .
  • projection 26 is generally conical.
  • FIGS. 2 and 3 show an aspect in which the protrusion 26 has a conical shape
  • the shape of the protrusion 26 is not particularly limited.
  • the protrusions 26 may be cylindrical, polygonal prismatic, hemispherical, bell-shaped, conical, polygonal pyramidal, and combinations thereof.
  • Polygonal prisms include triangular prisms, quadrangular prisms, pentagonal prisms, hexagonal prisms, and the like.
  • Polygonal pyramids include triangular pyramids, square pyramids, pentagonal pyramids, hexagonal pyramids, and the like.
  • the shape of the protrusion 26 is preferably hemispherical, bell-shaped, or conical in terms of better color visibility. Also, all the protrusions 26 may have substantially the same shape, or may have two or more types of shapes. The shape of the protrusion 26 can be confirmed by observing the laminate 20 with an SEM or the like.
  • the height of the protrusions 26 is not particularly limited, but is preferably 150 to 10000 nm, more preferably 400 to 5000 nm, from the viewpoint of excellent color visibility.
  • the height of the projection is obtained by averaging the heights of 100 projections observed by the above method.
  • the average interval of the protrusions 26 is not particularly limited, but is preferably 400 to 5000 nm from the viewpoint of excellent color visibility.
  • the average distance between the protrusions 26 is obtained by observing the laminate 20 with an SEM from a direction perpendicular to the substrate, measuring the distance between the protrusions 26 in the obtained image, and averaging the distances.
  • the distance between the protrusions 26 is the distance from the center of the protrusion 26 to the center of another protrusion 26 when viewed from the direction perpendicular to the base material.
  • the average distance between protrusions is defined as the average distance between the closest protrusions by analyzing the image obtained by the above method. Specifically, 100 intervals between the protrusions are measured, and the arithmetic mean is obtained.
  • the regular reflectance on the side of the laminate 20 on which the pattern 28 is arranged is preferably 4.00% or less, more preferably 1.00% or less, and even more preferably 0.50% or less.
  • the diffuse reflectance of the side of the laminate 20 on which the pattern 28 is arranged is preferably 2.00% or less, more preferably 0.5% or less, and even more preferably 0.30% or less.
  • the regular reflectance and diffuse reflectance are values measured using CM-700D manufactured by Konica Minolta, Inc.
  • the laminate Since the laminate has excellent color visibility, it can be preferably used for devices related to optics.
  • the laminate when a black pigment is used as the colorant, the laminate has a high absorptivity of visible light with a wavelength of 400 to 700 nm and suppresses reflection, so it can be used as an antireflection member for various apparatuses and devices.
  • Various apparatuses and devices are not particularly limited, and include display apparatuses, photographing apparatuses, imaging elements, various sensors, microscopes, telescopes, and the like. Among others, it can be preferably used as an antireflection member for an LED display.
  • the position of the laminate in the LED display is not particularly limited as long as it does not hinder the visibility of light emitted from the LED. It is preferably a front member provided in.
  • the front member of the LED display includes, for example, the front member used in the LED display described in paragraphs 0032 to 0042 of JP-A-2014-209198, the contents of which are incorporated herein.
  • the antireflection member of the LED display can also be used as a member for removing stray light of the light of the LED display.
  • Example 1 A method of forming the colored layer 1 (colorant: CNT (carbon nanotube)) representatively used in Example 1 will be described below. (Preparation of CNT dispersion) The components shown below were placed in a 300 cc glass bottle and dispersed for 1 hour using a paint conditioner using zirconia beads (0.5 mm ⁇ ) as media to obtain a carbon nanotube (CNT) dispersion.
  • CNT carbon nanotube
  • CNT carbon nanotube
  • Styrene-acrylic polymer manufactured by Johnson Polymer Co., Joncryl 683
  • ⁇ Butyl acetate 92.0 g
  • a colored layer coating liquid 1 was obtained by mixing the components shown below.
  • -Colored layer coating liquid 1- ⁇ CNT dispersion liquid 20 parts by mass ⁇ Propyl acetate: 7.37 parts by mass ⁇ Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.): 5.63 parts by mass ⁇ Benzyl methacrylate / methacrylic acid random copolymer (mol Ratio 70/30, weight average molecular weight 5,000) 45% by mass propylene glycol monomethyl ether acetate solution: 18.19 parts by mass IRGACURE OXE-02 (manufactured by BASF): 0.55 parts by mass Megafac (registered trademark) ) F551 (manufactured by Dainippon Ink and Chemicals Co., Ltd.): 0.09 parts by mass
  • Colored layer coating solution 1 was applied using a slit-like nozzle onto a polyethylene terephthalate (PET) film (manufactured by Toray Industries, Inc., 16KS40) (temporary support 1) having a thickness of 16 ⁇ m, and the formed coating film was heated at 100° C. for 3 hours. dried for a minute. Thus, a colored layer 1 having a thickness of 10.0 ⁇ m was formed on the temporary support 1 to obtain a temporary support with the colored layer 1 (colored film 1). Using a UV spectrophotometer (manufactured by Shimadzu Corporation, model number "UV-1800”), the transmittance of the obtained colored film 1 is measured, and the transmittance of the temporary support 1 measured in advance is subtracted.
  • PTT polyethylene terephthalate
  • 16KS40 temporary support 1 having a thickness of 16 ⁇ m
  • the transmittance of the colored layer 1 was calculated. As a result, the transmittance of the colored layer 1 at a wavelength of 550 nm was 1.0%. Therefore, the optical density of the colored layer 1 at a wavelength of 550 nm was 2.0.
  • Photosensitive layer coating liquid 1 - ⁇ Polymer 1 (styrene acid / acrylic acid copolymer, molar ratio: 63/37, manufactured by Toagosei Co., Ltd., ARUFON UC3910): 20.0 parts by mass ⁇ 9-methylacridine (manufactured by Tokyo Chemical Industry Co., Ltd.): 2 .5 parts by mass Propylene glycol monomethyl ether acetate: 41.4 parts by mass Methyl ethyl ketone: 36.0 parts by mass Megafac (registered trademark) F551 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) (surfactant): 0 .1 part by mass
  • a slit-shaped nozzle is used to apply photosensitive layer coating liquid 1 onto a 16 ⁇ m thick PET film (manufactured by Toray, 16FB40) (temporary support 2), and the formed coating film is dried at 100° C. for 3 minutes. bottom.
  • a photosensitive layer 1 having a film thickness of 4.0 ⁇ m was formed on the temporary support 2 to obtain a temporary support with a photosensitive layer 1 (photosensitive film 1).
  • the transmittance of the photosensitive layer 1 was measured in the same manner as above, the transmittance of the photosensitive layer 1 at a wavelength of 550 nm was 99.7%. Therefore, the optical density of the photosensitive layer 1 at a wavelength of 550 nm was 0.0013.
  • a method of forming a transfer film representatively used in Example 1 will be described below.
  • a laminated transfer film 1 was obtained using a laminator Lamic II type (manufactured by Hitachi Industries, Ltd.) so that the colored layer of the colored film 1 and the photosensitive layer 1 of the photosensitive film 1 faced each other.
  • the lamination was carried out under pressure and heating conditions of a line pressure of 100 N/cm, an upper roll of 100° C. and a lower roll of 100° C., and the conveying speed was 4 m/min.
  • the transfer film 1 had a layer structure of temporary support 1/colored layer 1/photosensitive layer 1/temporary support 2.
  • Example 1 The pattern forming method of Example 1 will be described below as a representative example.
  • the temporary support 1 of the transfer film 1 was peeled off to expose the colored layer 1 .
  • the surface of the exposed colored layer is superimposed on a glass substrate (Eagle XG manufactured by Corning, 10 cm square, thickness 0.7 mm), and a linear pressure of 100 N is applied using a laminator Lamic II type (manufactured by Hitachi Industries, Ltd.). /cm, an upper roll of 100°C, and a lower roll of 100°C.
  • Laminate 1 had a layer structure of glass substrate/colored layer 1/photosensitive layer 1/temporary support 2.
  • a mask 1 having the following four regions was prepared as an exposure mask.
  • ⁇ Region 1 A pattern region in which square openings of 400 nm on each side are arranged at intervals of 800 nm vertically and horizontally (opening ratio 25%)
  • ⁇ Region 2 A pattern region in which square openings of 800 nm on each side are arranged at intervals of 1600 nm vertically and horizontally (opening ratio 25%)
  • ⁇ Region 3 A pattern region in which square openings of 1600 nm on each side are arranged at intervals of 3200 nm vertically and horizontally (opening ratio 25%)
  • ⁇ Region 4 A pattern region in which square openings with a side of 3200 nm are arranged at intervals of 6400 nm vertically and horizontally (opening ratio 25%)
  • interval means the length from the center position of an opening to the center position of an adjacent opening.
  • the temporary support 2 is peeled off from the laminate 1, and an exposure machine (manufactured by Ushio Inc., alignment exposure machine MAP-1200, manufactured by Ushio Inc.) having an ultrahigh-pressure mercury lamp is used to photosensitize from the side opposite to the glass substrate through a mask.
  • Layer 1 was exposed.
  • the exposure light was i-line (wavelength: 365 nm), and the exposure amount was 200 mJ/cm 2 .
  • the gap between the mask and the photosensitive layer 1 was 0 ⁇ m (contact exposure).
  • the laminate 1 subjected to the exposure step was immersed in a 1% by mass sodium carbonate aqueous solution (liquid temperature: 25° C.) as a developer for 60 seconds (dip development). After being immersed in the developer, the laminate 1 was immersed in pure water for 20 seconds, shower-washed with pure water, and blown with air to form a pattern. Laminate 1 used in Example 1 was obtained through the above procedure.
  • Example 2 to 10 ⁇ Production of laminates used in Examples 2 to 10>
  • the laminates used in Examples 2 to 10 were prepared in the same manner as in Example 1 except that the materials, addition amounts, and film thicknesses of the photosensitive layer and the colored layer were as described in Table 1 below. evaluated.
  • the materials for the photosensitive layer shown in Table 1 below and the method for producing the colored layer 2 (coloring agent: CB (carbon black)) used in Example 6 are described below.
  • Polymer 2 As polymer 2, the following was used. - Methacrylic acid/allyl methacrylate copolymer (molar ratio: 20/80, weight average molecular weight: 40,000, degree of dispersion: 2.6)
  • Polymer 3 As polymer 3, the following was used.
  • Synthesis of polymer 3 was carried out according to the following procedure. 200 g of propylene glycol monomethyl ether and 50 g of propylene glycol monomethyl ether acetate were placed in a flask and heated to 90° C. under a nitrogen stream. For this liquid, 192.9 g of cyclohexyl methacrylate, 4.6 g of methyl methacrylate, and 89.3 g of methacrylic acid were dissolved in 60 g of propylene glycol monomethyl ether acetate, and a polymerization initiator V-601 (FUJIFILM Wako Pure Chemical Industries, Ltd.
  • Polymer 4 As the polymer 4, the one shown below was used.
  • Synthesis of polymer 4 was carried out according to the following procedure.
  • a flask was charged with 82.4 g of propylene glycol monomethyl ether and heated to 90° C. under a nitrogen stream.
  • a solution prepared by dissolving 5.4 g of propylene glycol monomethyl ether acetate (manufactured by Yakusha) in 43.6 g of propylene glycol monomethyl ether acetate was simultaneously added dropwise over 3 hours.
  • V-601 was added three times at intervals of 1 hour. After that, the mixture was reacted at 90° C. for 3 hours. After the reaction, it was diluted with 58.4 g of propylene glycol monomethyl ether acetate and 11.7 g of propylene glycol monomethyl ether. After dilution, the reaction solution was heated to 100° C. under an air stream, and 0.53 g of tetraethylammonium bromide and 0.26 g of p-methoxyphenol were added. To this reaction solution, 25.5 g of glycidyl methacrylate (manufactured by NOF Corporation, Blenmer GH) was added dropwise over 20 minutes.
  • glycidyl methacrylate manufactured by NOF Corporation, Blenmer GH
  • Polymerizable compound As the polymerizable compound, the following were used. ⁇ KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
  • a colored layer coating liquid 2 was obtained by mixing the components shown below.
  • the colored layer coating solution 2 was applied onto the temporary support 1 using a slit nozzle, and the formed coating film was dried at 100° C. for 3 minutes. Thus, a colored layer 2 having a film thickness of 10.0 ⁇ m was formed on the temporary support 1 to obtain a temporary support with the colored layer 2 (colored film 2).
  • the transmittance of the colored layer 2 was measured in the same manner as above, the transmittance of the colored layer 2 at a wavelength of 550 nm was 1.0%. Therefore, the optical density of the colored layer 2 at a wavelength of 550 nm was 2.0.
  • the light emitted from the high-pressure mercury lamp has a dominant wavelength of 365 nm and strong line spectra at 254 nm, 313 nm, 405 nm, and 436 nm.
  • the carboxy group consumption rate is obtained by the following formula.
  • Carboxy group consumption rate (%): ⁇ (carboxy group amount before exposure - carboxy group amount after exposure)/carboxy group amount before exposure ⁇ x 100 (%) The higher the carboxyl group consumption rate, the more the decarboxylation reaction progresses.
  • the amount of carboxy groups in the solid content (photosensitive material) of the photosensitive layer coating solution used to form the photosensitive layer of each example was measured according to the following procedure. 1 g of the photosensitive material was dissolved in 63 ml of tetrahydrofuran, and 12 ml of ultrapure water was added thereto. Then, using an automatic titrator manufactured by Hiranuma Sangyo Co., Ltd., the resulting solution was titrated with an aqueous 0.1N-NaOH solution. The amount of carboxyl groups in the photosensitive material was calculated by converting the amount of carboxyl groups obtained by titration into the solid content concentration.
  • the laminate exposed using the mask 1 was evaluated for reflectance.
  • CM-700D manufactured by Konica Minolta Co., Ltd. is used to measure the surface reflectance on the side of the laminate having protrusions, and SCI (Specular Component Include) and SCE (Specular Component Exclude) are measured. got the value.
  • the measurement was performed in the range of 360 to 740 nm in increments of 10 nm, and the value at 550 nm was used as a representative value of the reflectance for evaluation.
  • the measurement of the surface reflectance was performed in the exposed area with the smallest opening among the areas where it was confirmed that the protrusions were formed in the evaluation of resolution.
  • the layered product exposed using the mask 1 was evaluated for color visibility. Specifically, the laminate was installed under a ceiling light (fluorescent lamp, luminance: 2500 cd/m 2 ), and visually evaluated from the left, right, top and bottom, and the color derived from the coloring agent contained in the colored portion was visually recognized. The properties were confirmed and evaluated according to the following evaluation criteria.
  • Table 1 shows the components and formulation of the photosensitive layer, the components and formulation of the colored layer, the measurement results, and the evaluation results of each example and each comparative example.
  • polymerizable compound represents the above polymerizable compound
  • photopolymerization initiator represents the above photopolymerization initiator.
  • transmission and “optical density” represent those measured by the above method.
  • molar ratio represents the ratio (%) of the molar amount of compound ⁇ to the molar amount of carboxy groups contained in the polymer.
  • average height and “average spacing” represent those measured by the above method.
  • transfer film 12 temporary support 14 photosensitive layer 16 colored layer 20 laminate 22 base material 24 colored layer 26 protrusion 28 pattern

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)
  • Decoration By Transfer Pictures (AREA)

Abstract

La présente invention aborde le problème consistant à fournir un film de transfert doté d'un support temporaire et d'une couche colorée contenant un agent colorant disposée sur le support temporaire, le film de transfert transférant une couche qui comprend la couche colorée située sur le support temporaire vers un substrat, et la couleur provenant de l'agent colorant sur le substrat étant facilement visible lorsqu'elle est exposée et développée. Ce film de transfert comporte, dans l'ordre suivant, un support temporaire, une couche photosensible contenant un composé A ayant un groupe carboxy, et une couche colorée contenant un agent colorant, la teneur du groupe carboxy étant réduite par irradiation avec des rayons lumineux actifs ou des rayons radioactifs.
PCT/JP2022/029588 2021-08-24 2022-08-02 Film de transfert et procédé de production de stratifié WO2023026786A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001013877A (ja) * 1999-06-30 2001-01-19 Fujitsu Ltd 平面型表示装置
JP2001350255A (ja) * 2000-06-08 2001-12-21 Hitachi Chem Co Ltd ブラックマトリックス形成用感光性フィルム
JP2010249927A (ja) * 2009-04-13 2010-11-04 Hitachi Chem Co Ltd パターン形成用材料、これを用いたフィルム状エレメント及びパターン形成方法
JP2016071342A (ja) * 2014-09-30 2016-05-09 富士フイルム株式会社 凹凸構造を有する物品の製造方法および凹凸構造を有する物品
WO2020040054A1 (fr) * 2018-08-23 2020-02-27 富士フイルム株式会社 Film de transfert, stratifié, et procédé de formation de motif

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001013877A (ja) * 1999-06-30 2001-01-19 Fujitsu Ltd 平面型表示装置
JP2001350255A (ja) * 2000-06-08 2001-12-21 Hitachi Chem Co Ltd ブラックマトリックス形成用感光性フィルム
JP2010249927A (ja) * 2009-04-13 2010-11-04 Hitachi Chem Co Ltd パターン形成用材料、これを用いたフィルム状エレメント及びパターン形成方法
JP2016071342A (ja) * 2014-09-30 2016-05-09 富士フイルム株式会社 凹凸構造を有する物品の製造方法および凹凸構造を有する物品
WO2020040054A1 (fr) * 2018-08-23 2020-02-27 富士フイルム株式会社 Film de transfert, stratifié, et procédé de formation de motif

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