WO2021182399A1 - Liquide d'élimination, kit, et dispositif à semi-conducteur - Google Patents

Liquide d'élimination, kit, et dispositif à semi-conducteur Download PDF

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Publication number
WO2021182399A1
WO2021182399A1 PCT/JP2021/009000 JP2021009000W WO2021182399A1 WO 2021182399 A1 WO2021182399 A1 WO 2021182399A1 JP 2021009000 W JP2021009000 W JP 2021009000W WO 2021182399 A1 WO2021182399 A1 WO 2021182399A1
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group
preferable
protective layer
surfactant
carbon atoms
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PCT/JP2021/009000
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English (en)
Japanese (ja)
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高桑　英希
嶋田　和人
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富士フイルム株式会社
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Priority to JP2022507180A priority Critical patent/JPWO2021182399A1/ja
Priority to CN202180019423.6A priority patent/CN115244470A/zh
Publication of WO2021182399A1 publication Critical patent/WO2021182399A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a remover, a kit and a semiconductor device.
  • an organic semiconductor device has an advantage that it can be manufactured by a simple process as compared with a conventional electronic device using an inorganic semiconductor such as silicon. Further, the material properties of an organic semiconductor can be easily changed by changing its molecular structure. In addition, there are a wide variety of materials, and it is thought that it will be possible to realize functions and elements that could not be achieved with inorganic semiconductors.
  • Organic semiconductors can be applied to electronic devices such as organic solar cells, organic electroluminescence displays, organic optical detectors, organic field effect transistors, organic field light emitting devices, gas sensors, organic rectifying elements, organic inverters, and information recording elements. There is sex. It is known that such patterning of an organic layer such as an organic semiconductor is performed using a laminate containing an organic layer and a layer such as a photosensitive layer (for example, a resist layer).
  • Patent Document 1 has an organic semiconductor film, a protective film on the organic semiconductor film, and a resist film on the protective film, and the resist film is an organic acid having a pKa of a generated acid of -1 or less.
  • a photosensitive resin composition containing a photoacid generator (A) that generates The body is listed.
  • the present invention is used for removing a protective layer contained in a pattern formed by etching a laminate containing a base material, an organic layer, a protective layer, and a photosensitive layer in this order, and the residue of the protective layer when the protective layer is removed.
  • ⁇ 1> Contains a surfactant, A removing liquid used for removing a protective layer contained in a pattern formed by etching a laminate containing a base material, an organic layer, a protective layer, and a photosensitive layer in this order.
  • ⁇ 2> The removing solution according to ⁇ 1>, wherein the HLB value of the above-mentioned surfactant calculated by the following Griffin method is 16.0 or less.
  • HLB value calculated by the Griffin method 20 ⁇ (formula amount of hydrophilic part in surfactant) / (molecular weight of surfactant)
  • ⁇ 4> The removing solution according to any one of ⁇ 1> to ⁇ 3>, wherein the surfactant contains a polyalkylene glycol structure.
  • ⁇ 5> The removing solution according to any one of ⁇ 1> to ⁇ 4>, wherein the surfactant contains a polyethylene glycol structure and an aliphatic hydrocarbon group having 8 or more carbon atoms.
  • ⁇ 6> The removing solution according to any one of ⁇ 1> to ⁇ 5>, wherein the surfactant contains a polyethylene glycol structure and an alkyl group having 8 or more carbon atoms.
  • ⁇ 7> The removing liquid according to any one of ⁇ 1> to ⁇ 6>, which contains water.
  • ⁇ 8> The removing solution according to any one of ⁇ 1> to ⁇ 7>, wherein the protective layer contains a surfactant containing an acetylene group.
  • ⁇ 9> The removing liquid according to any one of ⁇ 1> to ⁇ 8>, wherein the protective layer contains a water-soluble resin.
  • the composition used for forming the protective layer contains a water-soluble resin and a surfactant.
  • ⁇ 12> The kit according to ⁇ 10> or ⁇ 11>, wherein the surfactant contained in the composition used for forming the protective layer is a surfactant containing an acetylene group.
  • a semiconductor device including a pattern in which the protective layer is removed from the above pattern by the removing liquid according to any one of ⁇ 1> to ⁇ 9>.
  • the present invention is used for removing a protective layer contained in a pattern formed by etching a laminate containing a base material, an organic layer, a protective layer, and a photosensitive layer in this order, and the protective layer at the time of removing the protective layer.
  • the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
  • the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
  • the notation that does not describe substitution or non-substitution means to include those having a substituent as well as those having no substituent. For example, when simply described as "alkyl group”, this includes both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group).
  • alkyl group when simply described as “alkyl group”, this means that it may be chain-like or cyclic, and in the case of chain-like, it may be linear or branched. These are also synonymous with other groups such as “alkenyl group”, “alkylene group” and “alkenylene group”.
  • exposure means not only drawing using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Examples of energy rays used for drawing include emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, active rays such as extreme ultraviolet rays (EUV light) and X-rays, and particle beams such as electron beams and ion beams. Be done.
  • light includes not only light having wavelengths in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, and infrared regions, electromagnetic waves, but also radiation, unless otherwise specified. Radiation includes, for example, microwaves, electron beams, extreme ultraviolet rays (EUV), and X-rays. Further, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. As these lights, monochrome light (single wavelength light) that has passed through an optical filter may be used, or light containing a plurality of wavelengths (composite light) may be used.
  • (meth) acrylate means both “acrylate” and “methacrylate”, or either
  • (meth) acrylic means both “acrylic” and “methacryl”, or
  • (meth) acryloyl means both “acryloyl” and “methacryloyl”, or either.
  • the solid content in the composition means other components other than the solvent, and the content (concentration) of the solid content in the composition is, unless otherwise specified, based on the total mass of the composition. It is represented by the mass percentage of other components excluding the solvent.
  • the temperature is 23 ° C.
  • the atmospheric pressure is 101325 Pa (1 atm)
  • the relative humidity is 50% RH.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are shown as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
  • GPC measurement gel permeation chromatography
  • Mw and Mn are shown as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
  • Mw and Mn for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel are used as columns. It can be obtained by using Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
  • the measurement is carried out using THF (tetrahydrofuran) as the eluent.
  • a UV ray (ultraviolet) wavelength 254 nm detector is used for detection in GPC measurement.
  • the positional relationship of each layer constituting the laminated body is described as "upper” or “lower”
  • the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other.
  • the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as “upper”.
  • the opposite direction is referred to as "down”. It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "upward" direction in the present specification may be different from the vertical upward direction.
  • the removing liquid of the present invention contains a surfactant (hereinafter, also referred to as "surfactant for removing liquid”), and the laminate containing the base material, the organic layer, the protective layer, and the photosensitive layer in this order is etched. It is used to remove the protective layer contained in the pattern.
  • the etched pattern is a pattern obtained by etching the organic layer and the protective layer.
  • the etched pattern is preferably a pattern obtained by etching the pattern made of the photosensitive layer as an etching resist.
  • the pattern composed of the photosensitive layer is formed by, for example, exposure and development.
  • the etched pattern is a pattern including a base material, an organic layer and a protective layer in this order, and the pattern composed of the photosensitive layer may be further contained on the side of the protective layer opposite to the organic layer. It is not necessary to include the pattern composed of the photosensitive layer. That is, the pattern made of the photosensitive layer may be completely removed by the etching, or the pattern made of the photosensitive layer may remain. The details of the laminate and the method of forming the etched pattern will be described later.
  • the removing liquid of the present invention it is effective in removing the residue of the protective layer at the time of removing the protective layer.
  • the mechanism by which the above effect is obtained is unknown, protection by the removing liquid is used as the removing liquid used for removing the protective layer by using the removing liquid of the present invention which is a removing liquid containing a surfactant for the removing liquid. It is presumed that the solubility of the layer is improved and the residue after removal of the protective layer is suppressed.
  • Patent Document 1 does not describe the use of a removing liquid containing a surfactant as the removing liquid used for removing the protective layer.
  • the surfactant contained in the removing liquid refers to a component contained in the removing liquid, which lowers the surface tension of the removing liquid as compared with the removing liquid containing no such component.
  • the surfactant for the removing liquid may be either an ionic surfactant or a nonionic surfactant, but from the viewpoint of the influence on the organic layer, the nonionic surfactant is preferable.
  • the HLB value of the surfactant for the removing liquid calculated by the following Griffin method is preferably 16.0 or less.
  • HLB value calculated by the Griffin method 20 ⁇ (formula amount of hydrophilic part in surfactant) / (molecular weight of surfactant)
  • the HLB value is preferably 15.0 or less, more preferably 14.0 or less, and further preferably 13.0 or less.
  • the lower limit of the HLB value is preferably 8.0 or more, more preferably 8.5 or more, and further preferably 9.0 or more.
  • the polyalkylene glycol structure is not particularly limited, and examples thereof include a structure represented by the following formula (P-1). Wherein (P-1), are each R P independently represents an alkylene group, n represents an integer of 2 or more, two * each independently represent a bonding site with the other structures.
  • R P represents an alkylene group, preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, an ethylene group or a propylene group is particularly
  • an ethylene group is most preferred. That is, as the polyalkylene glycol structure, an ethylene glycol structure or a propylene glycol structure is preferable, and an ethylene glycol structure is more preferable.
  • n pieces of R P may be different even respectively identical.
  • n represents an integer of 2 or more, preferably an integer of 10 to 2,000, and more preferably an integer of 50 to 1,000.
  • the surfactant for the removing liquid preferably contains an aliphatic hydrocarbon group having 8 or more carbon atoms (hereinafter, also referred to as "aliphatic group R").
  • the number of carbon atoms in the aliphatic group R is preferably 8 to 50, more preferably 8 to 40, and even more preferably 10 to 30.
  • the aliphatic group R is preferably a saturated aliphatic hydrocarbon group having 8 or more carbon atoms, and more preferably an alkyl group having 8 or more carbon atoms. The preferred carbon numbers of these groups are as described above.
  • the aliphatic group R may have a substituent as long as the effect of the present invention can be obtained. Further, an embodiment in which an aliphatic hydrocarbon group having 8 or more carbon atoms is unsubstituted is also one of the preferred embodiments of the present invention.
  • the surfactant for the removing liquid preferably contains a polyethylene glycol structure and an aliphatic hydrocarbon group having 8 or more carbon atoms.
  • the number of repetitions of the ethylene glycol structure in the polyethylene glycol structure may be 2 or more, preferably 10 to 2,000, and more preferably 50 to 1,000.
  • the preferred embodiment of the aliphatic hydrocarbon group having 8 or more carbon atoms is the same as the preferred embodiment of the aliphatic group R described above.
  • the surfactant for the removing liquid preferably contains a polyethylene glycol structure and an alkyl group having 8 or more carbon atoms.
  • the surfactant for the removing liquid is preferably a compound represented by any of the following formulas (Z-1) to (Z-4).
  • (Z-1) ⁇ formula (Z-4) are each R P independently represents an alkylene group, n represents an integer of 2 or more, R Z each independently having 8 or more aliphatic carbon Represents a hydrocarbon group.
  • (Z-1) ⁇ formula (Z-4), each R P and n have the same meanings as R P and n in the formula (P-1), a preferable embodiment thereof is also the same.
  • the preferred embodiment of R Z is the same as the preferred embodiment of the above-mentioned aliphatic group R.
  • the surfactant for the removing liquid does not contain a fluorine atom, a silicon atom, and a phosphoric acid ester structure.
  • the molecular weight (weight average molecular weight when having a molecular weight distribution) of the surfactant for the removing liquid is preferably 200 to 1,000, and more preferably 250 to 500.
  • a commercially available product may be used as the surfactant for the removing liquid.
  • Commercially available products include EMALEX 710 (manufactured by Nippon Emulsion Co., Ltd.), Pionin D-1007, Pionin D-1105, Pionin D-1110, Pionin D-1420, Pionin D-2104-D (above, Takemoto Oil & Fat Co., Ltd.). (Manufactured by), Emargen 220 (manufactured by Kao Chemical Co., Ltd.), etc., but the present invention is not limited thereto.
  • the content of the surfactant for the removing liquid is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, and 0.4% by mass, based on the total mass of the removing liquid. It is more preferably about 8% by mass, and even more preferably 1.2 to 4% by mass.
  • the surfactant for the removing liquid one type may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the total amount is preferably in the above range. By using two or more kinds of surfactants for the removing liquid in combination, for example, the storage stability of the removing liquid itself is improved.
  • the removing liquid preferably further contains a solvent.
  • the solvent include water, an organic solvent or a mixture thereof, and it is preferable that the solvent contains water.
  • the content of water with respect to the total mass of the removing liquid is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. preferable.
  • the upper limit of the content is not particularly limited, but may be 99.95% by mass or less.
  • the content of water with respect to the total mass of the solvent is preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more. More preferred.
  • the upper limit of the content is not particularly limited, but may be 100% by mass or less.
  • the removing liquid may further contain a water-soluble solvent.
  • the removal liquid may further contain a water-soluble solvent.
  • water, a mixture of water and a water-soluble solvent, and a water-soluble solvent may be collectively referred to as an aqueous solvent.
  • the water-soluble solvent an organic solvent having a solubility in water at 23 ° C. of 1 g or more is preferable, an organic solvent having a solubility of 10 g or more is more preferable, and an organic solvent having a solubility of 30 g or more is further preferable.
  • the water-soluble solvent include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol and glycerin; ketone solvents such as acetone; and amide solvents such as formamide.
  • the removing liquid may be in a form that substantially does not contain components other than the solvent and the surfactant for the removing liquid.
  • the total content of the solvent and the surfactant for the removing liquid is preferably 98% by mass or more, more preferably 99% by mass or more, and 99.9% by mass, based on the total mass of the removing liquid. It is more preferably mass% or more.
  • the upper limit of the content is not particularly limited, and may be 100% by mass. Further, in the embodiment in which the removing liquid contains water, it is also possible to make the embodiment substantially free of components other than water and the surfactant for the removing liquid.
  • the total content of water and the surfactant for the removing liquid is preferably 98% by mass or more, more preferably 99% by mass or more, and 99.9% by mass, based on the total mass of the removing liquid. It is more preferably mass% or more.
  • the upper limit of the content is not particularly limited, and may be 100% by mass.
  • the removing liquid preferably has a viscosity of 1.0 mPa ⁇ s or less, more preferably 0.8 mPa ⁇ s or less, further preferably 0.75 mPa ⁇ s or less, and has a viscosity of 0.75 mPa ⁇ s or less. It is particularly preferably 0.72 mPa ⁇ s or less.
  • the lower limit of the viscosity is not particularly limited, and can be, for example, 0.10 mPa ⁇ s or more.
  • the viscosity can be measured by a known method, and is measured by, for example, a RE-80L type rotational viscometer manufactured by Toki Sangyo Co., Ltd.
  • the rotation speed may be set as appropriate, but can be set to, for example, 100 rpm.
  • the viscosity of the removal liquid is adjusted, for example, by the structure of the compound contained in the removal liquid, the temperature of the removal liquid, the mixing ratio of the solvent contained in the removal liquid, and the like.
  • the temperature of the removal liquid may be adjusted for the purpose of keeping the viscosity of the removal liquid in the above range.
  • the temperature of the removing liquid is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, further preferably 40 ° C. or higher, and particularly preferably 50 ° C. or higher.
  • the upper limit of the temperature can be, for example, 100 ° C. or lower, preferably 90 ° C. or lower, and more preferably 80 ° C. or lower.
  • the laminate used in the present invention will be described in detail.
  • the laminate used in the present invention includes a base material, an organic layer, a protective layer and a photosensitive layer in this order.
  • the photosensitive layer is preferably subjected to development using a developing solution.
  • the protective layer is used for removal using the removal liquid of the present invention.
  • FIG. 1 is a schematic cross-sectional view schematically showing an example of a processing process of a laminated body according to a preferred embodiment of the present invention.
  • the organic layer 3 (for example, an organic semiconductor layer) is arranged on the base material 4 as in the example shown in FIG. 1 (a).
  • the protective layer 2 that protects the organic layer 3 is arranged on the surface of the protective layer 2 in contact with the protective layer 2.
  • Another layer may be provided between the organic layer 3 and the protective layer 2, but from the viewpoint that the effect of the present invention can be more easily obtained, the organic layer 3 and the protective layer 2 are in direct contact with each other.
  • an example of a preferred embodiment is given.
  • the photosensitive layer 1 is arranged on the protective layer.
  • the photosensitive layer 1 and the protective layer 2 may be in direct contact with each other, or another layer may be provided between the photosensitive layer 1 and the protective layer 2.
  • FIG. 1B shows an example of a state in which a part of the photosensitive layer 1 is exposed and developed.
  • the photosensitive layer 1 is partially exposed by a method such as using a predetermined mask, and after the exposure, the photosensitive layer 1 is removed and exposed by developing with a developing solution such as an organic solvent.
  • the photosensitive layer 1a after development is formed.
  • the protective layer 2 remains because it is difficult to be removed by the developer, and the organic layer 3 is protected from damage by the developer by the remaining protective layer 2.
  • FIG. 1C shows an example of a state in which a part of the protective layer 2 and the organic layer 3 is removed.
  • the removing portion 5a is formed in the protective layer 2 and the organic layer 3. Will be done. In this way, the organic layer 3 can be removed in the removing portion 5a. That is, the organic layer 3 can be patterned.
  • FIG. 1C is an example of a pattern formed by etching a laminate containing a base material, an organic layer, a protective layer, and a photosensitive layer in this order, and the removing liquid of the present invention is, for example, In the state shown in FIG. 1 (c), it is used for removing the protective layer.
  • FIG. 1C shows a state in which the photosensitive layer 1a remains after development, but the photosensitive layer 1a after development may be removed by, for example, a dry etching process or the like.
  • FIG. 1D shows an example in which the photosensitive layer 1a and the protective layer 2 are removed after the patterning.
  • the photosensitive layer 1a and the protective layer 2 on the processed organic layer 3a are removed by washing the photosensitive layer 1a and the protective layer 2 in the laminated body in the state shown in FIG. 1C with the removing liquid of the present invention. Will be done.
  • the cleaning with the removal liquid of the present invention may be performed a plurality of times.
  • further rinsing may be performed with pure water or the like.
  • the surfactant for the removing liquid is removed from the surface of the laminate after cleaning.
  • the laminate used in the present invention includes a base material.
  • the base material that may be contained in the laminate is formed of, for example, various materials such as silicon, quartz, ceramic, glass, polyester film such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET), and polyimide film. Any base material may be selected depending on the intended use.
  • PEN polyethylene naphthalate
  • PET polyethylene terephthalate
  • Any base material may be selected depending on the intended use.
  • a base material formed of a flexible material can be used.
  • the base material may be a composite base material formed of a plurality of materials or a laminated base material in which a plurality of materials are laminated.
  • the shape of the base material is not particularly limited and may be selected according to the intended use, and examples thereof include a plate-shaped base material (board).
  • the thickness of the substrate is also not particularly limited.
  • the laminate in the present invention contains an organic layer.
  • the organic layer is a layer containing an organic material.
  • the specific organic material is appropriately selected according to the use and function of the organic layer. Assumed functions of the organic layer include, for example, semiconductor characteristics, light emission characteristics, photoelectric conversion characteristics, light absorption characteristics, electrical insulation, ferroelectricity, transparency, and insulation.
  • the organic layer may be contained above the base material, the base material may be in contact with the organic layer, or another layer may be further contained between the organic layer and the base material. May be.
  • the thickness of the organic layer is not particularly limited and varies depending on the type of electronic device used and the like, but is preferably 1 nm to 50 ⁇ m, more preferably 1 nm to 5 ⁇ m, and further preferably 1 nm to 500 nm.
  • the organic layer is an organic semiconductor layer
  • the organic semiconductor layer is a layer containing an organic material exhibiting the characteristics of a semiconductor.
  • the organic semiconductor layer is an organic layer containing an organic semiconductor, and the organic semiconductor is an organic compound exhibiting the characteristics of a semiconductor. Similar to the case of semiconductors made of inorganic compounds, organic semiconductors include p-type semiconductors that conduct holes as carriers and n-type semiconductors that conduct electrons as carriers.
  • the ease of carrier flow in the organic semiconductor layer is represented by the carrier mobility ⁇ . Although it depends on the application, in general, the carrier mobility is preferably high, preferably 10-7 cm 2 / Vs or more, more preferably 10-6 cm 2 / Vs or more, and 10-5 cm 2 or more. It is more preferably / Vs or more.
  • the carrier mobility can be determined based on the characteristics when the field effect transistor (FET) element is manufactured and the measured value by the flight time measurement (TOF) method.
  • the p-type organic semiconductor that can be used for the organic semiconductor layer, any material may be used as long as it has hole transportability.
  • the p-type organic semiconductor is preferably any one of a p-type ⁇ -conjugated polymer, a condensed polycyclic compound, a triarylamine compound, a hetero 5-membered ring compound, a phthalocyanine compound, a porphyrin compound, carbon nanotubes, and graphene. Further, as the p-type organic semiconductor, a plurality of kinds of compounds among these compounds may be used in combination.
  • the p-type organic semiconductor is more preferably at least one of a p-type ⁇ -conjugated polymer, a condensed polycyclic compound, a triarylamine compound, a hetero 5-membered ring compound, a phthalocyanine compound, and a porphyrin compound, and more preferably. It is at least one of a p-type ⁇ -conjugated polymer and a condensed polycyclic compound.
  • the p-type ⁇ -conjugated polymer is, for example, substituted or unsubstituted polythiophene (for example, poly (3-hexylthiophene) (P3HT, manufactured by Sigma Aldrich Japan LLC)), polyselenophene, polypyrrole, polyparaphenylene, poly. Paraphenylene vinylene, polythiophene vinylene, polyaniline, etc.
  • Condensed polycyclic compounds include, for example, substituted or unsubstituted anthracene, tetracene, pentacene, anthradithiophene, hexabenzocoronene and the like.
  • Triarylamine compounds include, for example, m-MTDATA (4,4', 4''-Tris [(3-methylphenyl) biphenyllamine), 2-TNATA (4,4', 4''-Tris [2- naphthyl (phenyl) amine), NPD (N, N'-Di (1-naphthyl) -N, N'-diphenyl- (1,1'-biphenyl) -4,4'-diamine), TPD (N) , N'-Diphenyl-N, N'-di (m-tool) benzine), mCP (1,3-bis (9-carbazolyl) benzene), CBP (4,4'-bis (9-carbazolyl) -2 , 2'-biphenyl) and the like.
  • the hetero 5-membered ring compound is, for example, a substituted or unsubstituted oligothiophene, TTF (Tetrathiafulvalene), or the like.
  • the phthalocyanine compound is a substituted or unsubstituted phthalocyanine having various central metals, naphthalocyanine, anthracyanine, tetrapyrazinoporphyrazine and the like.
  • Porphyrin compounds are substituted or unsubstituted porphyrins having various central metals.
  • the carbon nanotube may be a carbon nanotube whose surface is modified with a semiconductor polymer.
  • n-type organic semiconductor that can be used for the organic semiconductor layer, any material may be used as long as it has electron transportability.
  • the n-type organic semiconductor is preferably a fullerene compound, an electron-deficient phthalocyanine compound, a fused polycyclic compound (naphthalene tetracarbonyl compound, perylene tetracarbonyl compound, etc.), a TCNQ compound (tetracyanoquinodimethane compound), and a polythiophene compound.
  • n-type organic semiconductor a plurality of kinds of compounds among these compounds may be used in combination.
  • the n-type organic semiconductor is more preferably at least one of a fullerene compound, an electron-deficient phthalocyanine compound, a fused polycyclic compound, and an n-type ⁇ -conjugated polymer, and particularly preferably a fullerene compound and a condensed polycyclic ring. It is at least one of a compound and an n-type ⁇ -conjugated polymer.
  • the fullerene compound means a substituted or unsubstituted fullerene, and the fullerenes are C 60 , C 70 , C 76 , C 78 , C 80 , C 82 , C 84 , C 86 , C 88 , C 90 , C 96. , C 116 , C 180 , C 240 , C 540 and the like.
  • the fullerene compound is preferably substituted or unsubstituted C 60 , C 70 , C 86 fullerene, and particularly preferably PCBM ([6,6] -phenyl-C61-butyric acid methyl ester, manufactured by Sigma Aldrich Japan GK.
  • the electron-deficient phthalocyanine compound is a substituted or unsubstituted phthalocyanine, naphthalocyanine, anthracyanine, tetrapyrazinoporphyrazine and the like having four or more electron-attracting groups bonded and having various central metals.
  • Electron-deficient phthalocyanine compounds include, for example, fluorinated phthalocyanine (F 16 MPc) and chlorinated phthalocyanine (Cl 16 MPc).
  • F 16 MPc fluorinated phthalocyanine
  • Cl 16 MPc chlorinated phthalocyanine
  • M represents a central metal
  • Pc represents a phthalocyanine.
  • naphthalene tetracarbonyl compound Any naphthalene tetracarbonyl compound may be used, but naphthalene tetracarboxylic acid anhydride (NTCDA), naphthalene bisimide compound (NTCDI), perinone pigment (Pigment Orange 43, Pigment Red 194, etc.) are preferable.
  • NTCDA naphthalene tetracarboxylic acid anhydride
  • NTCDI naphthalene bisimide compound
  • perinone pigment Pigment Orange 43, Pigment Red 194, etc.
  • perylenetetracarbonyl compound Any perylenetetracarbonyl compound may be used, but perylenetetracarboxylic dianhydride (PTCDA), perylenebisimide compound (PTCDI), and benzoimidazole fused ring (PV) are preferable.
  • PTCDA perylenetetracarboxylic dianhydride
  • PTCDI perylenebisimide compound
  • PV benzoimidazole fused ring
  • the TCNQ compound is a substituted or unsubstituted TCNQ and a compound in which the benzene ring portion of TCNQ is replaced with another aromatic ring or heterocycle.
  • the TCNQ compounds include, for example, TCNQ, TCNAQ (tetracyanoquinodimethane), TCN3T (2,2'-((2E, 2''E) -3', 4'-Alkyl subscribed-5H, 5''H. -[2,2': 5', 2''-terthiophene] -5,5''-diylidene) dimalononirile derivatives) and the like.
  • the polythiophene-based compound is a compound having a polythiophene structure such as poly (3,4-ethylenedioxythiophene).
  • the polythiophene-based compound is, for example, PEDOT: PSS (complex composed of poly (3,4-ethylenedioxythiophene) (PEDOT) and polystyrene sulfonic acid (PSS)).
  • a benzidine-based compound is a compound having a benzidine structure in the molecule.
  • Benzidine compounds include, for example, N, N'-bis (3-methylphenyl) -N, N'-diphenylbenzidine (TPD), N, N'-di-[(1-naphthyl) -N, N'-. Diphenyl] -1,1'-biphenyl) -4,4'-diamine (NPD) and the like.
  • a carbazole-based compound is a compound having a carbazole ring structure in the molecule.
  • Carbazole compounds include, for example, 4,4'-bis (N-carbazolyl) -1,1'-biphenyl (CBP).
  • the phenanthroline-based compound is a compound having a phenanthroline ring structure in the molecule, and is, for example, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP).
  • the pyridinephenyl ligand iridium-based compound is a compound having an iridium complex structure having a phenylpyridine structure as a ligand.
  • Pyridinephenyl ligands The iridium-based compounds include, for example, bis (3,5-difluoro-2- (2-pyridylphenyl- (2-carboxypyridyl) iridium (III) (FIrpic)) and tris (2-phenylpyridinato). ) Iridium (III) (Ir (ppy) 3 ) and the like.
  • the quinolinol ligand alumnium-based compound is a compound having an aluminum complex structure having a quinolinol structure as a ligand, and is, for example, tris (8-quinolinolato) aluminum.
  • the R in the formula may be any, but is hydrogen atom, substituted or unsubstituted, branched or linear alkyl group (preferably 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 12 carbon atoms). 1 to 8), substituted or unsubstituted aryl groups (preferably those having 6 to 30, more preferably 6 to 20, still more preferably 6 to 14).
  • Me represents a methyl group and M represents a metal atom.
  • the organic semiconductor contained in the organic semiconductor layer may be one type or two or more types. Further, the organic semiconductor layer may be a laminated or mixed layer of a p-type layer and an n-type layer.
  • the organic layer may be formed by either a vapor phase method or a liquid phase method.
  • a physical vapor deposition (PVD) method such as a vapor deposition method (vacuum vapor deposition method, molecular beam epitaxy method, etc.), a sputtering method, an ion plating method, or a chemical vapor deposition method such as a plasma polymerization method is used.
  • PVD physical vapor deposition
  • a growth (CVD) method can be used, with a vapor deposition method being particularly preferred.
  • the organic material is blended in a solvent to form a composition for forming an organic layer (composition for forming an organic layer). Then, this composition is supplied onto a substrate and dried to form an organic layer.
  • coating is preferable. Examples of supply methods include slit coating method, casting method, blade coating method, wire bar coating method, spray coating method, dipping (immersion) coating method, bead coating method, air knife coating method, curtain coating method, inkjet method, etc. Examples thereof include a spin coat method, a Langmuir-Blodgett (LB) method, and an edge cast method (for details, see Patent No. 6179930). It is more preferable to use the casting method, the spin coating method, and the inkjet method. Such a process makes it possible to produce an organic layer having a smooth surface and a large area at low cost.
  • LB Langmuir-Blodgett
  • an organic solvent is preferable.
  • the organic solvent include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene and 1,2-dichlorobenzene; for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like.
  • Ketone solvents for example, halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene; and esters such as ethyl acetate, butyl acetate, amyl acetate, etc.
  • halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene
  • esters such as ethyl acetate, butyl acetate, amyl acetate, etc.
  • Solvents such as, for example, methanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol; and ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole; for example. , N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, dimethylsulfoxide and other polar solvents. Only one kind of these solvents may be used, or two or more kinds may be used.
  • the proportion of the organic material in the composition for forming an organic layer is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, whereby a film having an arbitrary thickness can be formed.
  • a resin binder may be blended in the composition for forming an organic layer.
  • the material forming the film and the binder resin can be dissolved or dispersed in the above-mentioned suitable solvent to prepare a coating liquid, and a thin film can be formed by various coating methods.
  • Resin binders include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulphon, polymethylmethacrylate, polymethylacrylate, cellulose, polyethylene, and polypropylene, and their co-weights.
  • Examples thereof include photoconductive polymers such as coalescing, polyvinylcarbazole and polysilane, and conductive polymers such as polythiophene, polypyrrole, polyaniline and polyparaphenylene vinylene.
  • the resin binder may be used alone or in combination of two or more. Considering the mechanical strength of the thin film, a resin binder having a high glass transition temperature is preferable, and considering charge mobility, a resin binder having a structure containing no polar group or a conductive polymer is preferable.
  • the blending amount is preferably 0.1 to 30% by mass in the organic layer.
  • the resin binder may be used alone or in combination of a plurality of types. In the case of a combination of a plurality of types, it is preferable that the total amount thereof is within the above range.
  • the organic layer may be a blended film composed of a plurality of material types, using a single solution or a mixed solution to which various organic materials and additives are added.
  • a mixed solution using a plurality of types of semiconductor materials can be used.
  • the base material may be heated or cooled at the time of film formation, and it is possible to control the film quality and the packing of molecules in the film by changing the temperature of the base material.
  • the temperature of the base material is not particularly limited, but is preferably ⁇ 200 ° C. to 400 ° C., more preferably ⁇ 100 ° C. to 300 ° C., and even more preferably 0 ° C. to 200 ° C.
  • the characteristics of the formed organic layer can be adjusted by post-treatment. For example, it is possible to improve the properties by changing the morphology of the membrane and the packing of molecules in the membrane by heat treatment or exposure to a vaporized solvent. Further, by exposing to an oxidizing or reducing gas, solvent, substance or the like, or by using these methods in combination, an oxidation or reduction reaction can occur, and the carrier density in the membrane can be adjusted.
  • the protective layer in the present invention is used for removal using the removal liquid of the present invention.
  • Examples of the removing method include the methods described as a step of removing the protective layer using a removing liquid in the method for producing a laminate and the method for patterning an organic layer, which will be described later.
  • the protective layer used in the present invention preferably has a dissolution rate in the removing liquid of the present invention of 100 nm / s or more, more preferably 120 nm / s or more, and further preferably 150 nm / s or more. preferable.
  • the upper limit of the dissolution rate is not particularly limited, and can be, for example, 1,000 nm / s or less.
  • the dissolution rate is measured, for example, by the following method.
  • the photosensitive layer is removed from the laminate to prepare a laminate from which the photosensitive layer has been removed.
  • the photosensitive layer can be removed, for example, by removing the photosensitive layer with a developing solution without performing either exposure or heating.
  • the film thickness (film thickness A) of the laminate from which the photosensitive layer has been removed is measured.
  • the laminate from which the photosensitive layer has been removed is immersed in the removing liquid for 5 seconds and then taken out, and the film thickness (film thickness B) of the laminate is measured again. By dividing the difference between the film thickness A and the film thickness B by the immersion time (5 seconds), the dissolution rate (nm / s) of the protective layer in the removal liquid is calculated.
  • the thickness of the protective layer is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, further preferably 1.0 ⁇ m or more, and even more preferably 2.0 ⁇ m or more.
  • the upper limit of the thickness of the protective layer is preferably 10 ⁇ m or less, more preferably 5.0 ⁇ m or less, and even more preferably 3.0 ⁇ m or less.
  • the protective layer in the present invention is preferably a layer having a dissolution rate in a developing solution of 10 nm / s or less at 23 ° C., and more preferably 1 nm / s or less.
  • the lower limit of the dissolution rate is not particularly limited, and may be more than 0 nm / s.
  • the protective layer in the present invention preferably contains a polymer compound.
  • the protective layer preferably contains a water-soluble polymer compound, and more preferably contains a water-soluble resin.
  • the water-soluble resin refers to a resin that dissolves 1 g or more in 100 g of water at 23 ° C.
  • the water-soluble resin is preferably a resin that dissolves 5 g or more with respect to 100 g of water at 23 ° C., more preferably a resin that dissolves 10 g or more, and further preferably a resin that dissolves 30 g or more. There is no particular upper limit on the amount of dissolution, but it is practically about 100 g.
  • the water-soluble resin is preferably a resin containing a hydrophilic group, and examples of the hydrophilic group include a hydroxy group, a carboxy group, a sulfonic acid group, a phosphoric acid group, an amide group, and an imide group.
  • water-soluble resin examples include polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), and water-soluble polysaccharides (water-soluble cellulose (methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxy).
  • PVP polyvinylpyrrolidone
  • PVA polyvinyl alcohol
  • water-soluble polysaccharides water-soluble cellulose (methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxy).
  • PVP polyvinylpyrrolidone
  • PVA polyvinyl alcohol
  • water-soluble polysaccharides water-soluble cellulose (methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxy).
  • purulan or purulan derivatives
  • the protective layer preferably contains at least one selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, water-soluble polysaccharides, pullulan and pullulan derivatives among these resins, and polyvinylpyrrolidone and polyvinyl alcohol. And at least one selected from the group consisting of water-soluble polysaccharides.
  • the water-soluble polysaccharide is particularly preferably cellulose, more preferably hydroxyethyl cellulose.
  • the water-soluble resin contained in the protective layer is a resin containing a repeating unit represented by any of the formulas (P1-1) to (P4-1).
  • R P1 is hydrogen or methyl
  • R P2 represents a hydrogen atom or a methyl group
  • R p31 ⁇ R p33 independently, substituents or hydrogen Representing an atom
  • R p41 to R p49 independently represent a substituent or a hydrogen atom.
  • R P1 is preferably a hydrogen atom.
  • the resin containing the repeating unit represented by the formula (P1-1) may further contain a repeating unit different from the repeating unit represented by the formula (P1-1).
  • the resin containing the repeating unit represented by the formula (P1-1) preferably contains the repeating unit represented by the formula (P1-1) in an amount of 10 mol% to 100 mol% with respect to all the repeating units of the resin. , 30 mol% to 70 mol% is more preferable.
  • Examples of the resin containing the repeating unit represented by the formula (P1-1) include a resin containing two repeating units represented by the following formula (P1-2).
  • R P11 each independently represent a hydrogen atom or a methyl group
  • R P12 represents a substituent
  • np1 and np2 represent composition ratio in the molecule in mass.
  • R P11 has the same meaning as R P1 in formula (P1-1), preferable embodiments thereof are also the same.
  • (P1-2) include groups represented by -L P -T P as R P12.
  • L P is a linking group L to a single bond or later.
  • T P is a substituent, and examples of the substituent T described later can be mentioned.
  • an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms are more preferable).
  • an alkynyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, 6 to 18 carbon atoms).
  • np1 and np2 represent the composition ratio in the molecule on a mass basis, and are independently 10% by mass or more and less than 100% by mass. However, np1 + np2 does not exceed 100% by mass. When np1 + np2 is less than 100% by mass, it means that the copolymer contains other repeating units.
  • Resin containing a repeating unit represented by the formula (P2-1) is preferably a hydrogen atom.
  • the resin containing the repeating unit represented by the formula (P2-1) may further contain a repeating unit different from the repeating unit represented by the formula (P2-1).
  • the resin containing the repeating unit represented by the formula (P2-1) preferably contains the repeating unit represented by the formula (P2-1) in an amount of 10% by mass to 100% by mass based on the total mass of the resin. It is more preferable to contain 30% by mass to 70% by mass.
  • Examples of the resin containing the repeating unit represented by the formula (P2-1) include a resin containing two repeating units represented by the following formula (P2-2).
  • R P21 each independently represent a hydrogen atom or a methyl group
  • R P22 represents a substituent
  • mp1 and mp2 represent composition ratio in the molecule in mass.
  • R P21 has the same meaning as R P2 in formula (P2-1), preferable embodiments thereof are also the same.
  • P2-2 include groups represented by -L P -T P as R P22.
  • L P is a linking group L to a single bond or later.
  • T P is a substituent, and examples of the substituent T described later can be mentioned.
  • an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms are more preferable).
  • an alkynyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, 6 to 18 carbon atoms).
  • mp1 and mp2 represent the composition ratio in the molecule on a mass basis, and are independently 10% by mass or more and less than 100% by mass. However, mp1 + mp2 does not exceed 100% by mass. When mp1 + mp2 is less than 100% by mass, it means that the copolymer contains other repeating units.
  • R p31 to R p33 are each independently a hydrocarbon group, an acyl group, which may have a substituent,-(CH 2 CH 2 O) ma H, -CH 2 COONa or hydrogen. It preferably represents an atom, more preferably a hydrocarbon group, a hydrocarbon group having a hydroxy group as a substituent, an acyl group or a hydrogen atom, and even more preferably a hydrogen atom.
  • ma is or 2.
  • the number of carbon atoms of the hydrocarbon group which may have the above-mentioned substituent is preferably 1 to 10, and more preferably 1 to 4.
  • hydrocarbon group having a hydroxy group as a substituent a hydrocarbon group having one hydroxy group and having 1 to 10 carbon atoms is preferable, and a hydrocarbon group having one hydroxy group and having 1 to 4 carbon atoms is more preferable.
  • -CH 2 (OH), -CH 2 CH 2 (OH) or -CH 2 CH (OH) CH 3 are more preferred.
  • acyl group an alkylcarbonyl group having 1 to 4 carbon atoms of the alkyl group is preferable, and an acetyl group is more preferable.
  • the resin containing the repeating unit represented by the formula (P3-1) may further contain a repeating unit different from the repeating unit represented by the formula (P3-1).
  • the resin containing the repeating unit represented by the formula (P3-1) preferably contains the repeating unit represented by the formula (P3-1) in an amount of 10% by mass to 100% by mass based on the total mass of the resin. It is more preferable to contain 30% by mass to 70% by mass.
  • the hydroxy group described in the formula (P3-1) may be appropriately substituted with a substituent T or a group combining the substituent L with the substituent L. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the ring in the formula with or without the linking group L to form a ring.
  • RP41 to RP49 are independent hydrocarbon groups, acyl groups,-(CH 2 CH 2 O) ma H, -CH 2 COONa or hydrogen, which may have substituents, respectively. It preferably represents an atom, more preferably a hydrocarbon group, a hydrocarbon group having a hydroxy group as a substituent, an acyl group or a hydrogen atom, and even more preferably a hydrogen atom.
  • ma is 1 or 2.
  • the number of carbon atoms of the hydrocarbon group which may have the above-mentioned substituent is preferably 1 to 10, and more preferably 1 to 4.
  • the resin containing the repeating unit represented by the formula (P4-1) may further contain a repeating unit different from the repeating unit represented by the formula (P4-1).
  • the resin containing the repeating unit represented by the formula (P4-1) preferably contains the repeating unit represented by the formula (P4-1) in an amount of 10% by mass to 100% by mass based on the total mass of the resin.
  • the hydroxy group described in the formula (P4-1) may be appropriately substituted with a substituent T or a group combining the substituent L with the substituent L.
  • substituents T When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the ring in the formula with or without the linking group L to form a ring.
  • an alkyl group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms
  • an arylalkyl group preferably 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms. , 7 to 11 is more preferable
  • an alkenyl group (2 to 24 carbon atoms are preferable, 2 to 12 is more preferable, 2 to 6 is more preferable
  • an alkynyl group (2 to 12 carbon atoms is preferable and 2 to 6 are preferable).
  • 2 to 3 are more preferable), hydroxy group, amino group (preferably 0 to 24 carbon atoms, more preferably 0 to 12 and even more preferably 0 to 6), thiol group, carboxy group, aryl group (carbon).
  • the number 6 to 22 is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), an alkoxyl group (1 to 12 carbon atoms is preferable, 1 to 6 is more preferable, 1 to 3 is more preferable), and aryloxy.
  • Group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms
  • acyl group preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms
  • Acyloxy group preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms
  • allylloyl group preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms).
  • allyloyloxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11), carbamoyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, 1).
  • carbamoyl group preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, 1).
  • ⁇ 3 is more preferable
  • sulfamoyl group preferably 0 to 12 carbon atoms, more preferably 0 to 6 and even more preferably 0 to 3
  • sulfo group alkylsulfonyl group (preferably 1 to 12 carbon atoms, 1 to 3).
  • 6 is more preferable, 1 to 3 is more preferable), an arylsulfonyl group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), and a heteroaryl group (1 to 12 carbon atoms is more preferable).
  • 1 to 8 is more preferable, 2 to 5 is even more preferable, and a 5-membered ring or a 6-membered ring is preferably contained), a (meth) acryloyl group, a (meth) acryloyloxy group, a halogen atom (for example, a fluorine atom).
  • RN is a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and a hydrogen atom, a methyl group, an ethyl group, or a propyl group is preferable.
  • the alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be chain or cyclic, and may be linear or branched.
  • the substituent T When the substituent T is a group capable of taking a substituent, it may further have a substituent T.
  • the alkyl group may be an alkyl halide group, a (meth) acryloyloxyalkyl group, an aminoalkyl group or a carboxyalkyl group.
  • the substituent is a group capable of forming a salt such as a carboxy group or an amino group, the group may form a salt.
  • an alkylene group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms) and an alkenylene group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms are more preferable. 2-3 are more preferred), alkynylene groups (2-12 carbon atoms are preferred, 2-6 are more preferred, 2-3 are more preferred), (oligo) alkyleneoxy groups (alkylene groups in one repeating unit.
  • the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, further preferably 1 to 3, and the number of repetitions is preferably 1 to 50, more preferably 1 to 40), an arylene group (more preferably 1 to 30).
  • (oligo) alkyleneoxy group means a divalent linking group having one or more "alkyleneoxy” which is a constituent unit.
  • the carbon number of the alkylene chain in the structural unit may be the same or different for each structural unit.
  • the alkylene group may have a substituent T.
  • the alkylene group may have a hydroxy group.
  • the number of atoms contained in the linking group L is preferably 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30, excluding hydrogen atoms.
  • the number of connected atoms is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6.
  • the alkylene group, alkenylene group, alkynylene group, and (oligo) alkyleneoxy group may be chain-like or cyclic, and may be linear or branched.
  • the linking group is a group capable of forming a salt such as ⁇ NR N ⁇ , the group may form a salt.
  • water-soluble resin examples include polyethylene oxide, hydroxyethyl cellulose, carboxymethyl cellulose, water-soluble methylol melamine, polyacrylamide, phenol resin, styrene / maleic acid semi-ester, poly-N-vinylacetamide and the like.
  • a commercially available product may be used as the water-soluble resin, and the commercially available products include the Pittscol series (K-30, K-50, K-90, etc.) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. and UVITEC manufactured by BASF. Series (VA64P, VA6535P, etc.), Japan Vam & Poval Co., Ltd.
  • the resin described in International Publication No. 2016/175220 is cited and incorporated in the present specification.
  • the weight average molecular weight of the water-soluble resin is appropriately selected according to the type of the water-soluble resin.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the water-soluble resin are the values converted to polyether oxide by GPC measurement.
  • the weight average molecular weight is 10,000 to 100,000. Is preferable.
  • the upper limit of this numerical range is preferably 80,000 or less, and more preferably 60,000 or less. Further, the lower limit of this numerical range is preferably 13,000 or more, and more preferably 15,000 or more.
  • the weight average molecular weight is preferably 20,000 to 2,000,000.
  • the upper limit of this numerical range is preferably 1,800,000 or less, and more preferably 1,500,000 or less. Further, the lower limit of this numerical range is preferably 30,000 or more, and more preferably 40,000 or more.
  • the water-soluble resin is a resin containing a repeating unit represented by the formula (P3-1) or the formula (p4-1) (for example, a water-soluble polysaccharide)
  • the weight average molecular weight is 50,000 to 2 , 000,000 is preferable.
  • the upper limit of this numerical range is preferably 1,500,000 or less, and more preferably 1,300,000 or less.
  • the lower limit of this numerical range is preferably 70,000 or more, and more preferably 90,000 or more.
  • the molecular weight dispersion of the water-soluble resin is preferably 1.0 to 5.0, more preferably 2.0 to 4.0.
  • the protective layer is a water-soluble resin having a high molecular weight resin (for example, a water-soluble resin having a weight average molecular weight of 10,000 or more) and a weight average molecular weight smaller than the weight average molecular weight of the high molecular weight resin. It is also preferable that the weight average molecular weight of the low molecular weight resin is half or less of the weight average molecular weight of the high molecular weight resin. As a result, the low molecular weight resin is rapidly eluted in the removing liquid (particularly water), and the high molecular weight resin is easily removed starting from the portion where the low molecular weight resin is eluted. The effect of further reduction can be obtained. Further, when the protective layer is formed by using the protective layer, it is possible to suppress the occurrence of cracks in the protective layer.
  • a water-soluble resin having a weight average molecular weight of 10,000 or more for example, a water-soluble resin having a weight average molecular weight of 10,000 or more
  • the protective layer contains the high molecular weight resin and the low molecular weight resin has two peak tops (maximum values) when, for example, the molecular weight distribution of the protective layer or the entire water-soluble resin is measured. Judgment can be made based on whether or not the above can be confirmed.
  • the weight average molecular weight of the high molecular weight resin is preferably 20,000 or more, and preferably 45,000 or more.
  • the weight average molecular weight of the high molecular weight resin is preferably 2,000,000 or less, and may be 1,500,000 or less.
  • the upper limit of the molecular weight ratio is more preferably 0.3 or less, and further preferably 0.2 or less.
  • the lower limit of the molecular weight ratio is not particularly limited, but is preferably 0.001 or more, and may be 0.01 or more.
  • the molecular weight corresponding to one peak top is the other one. It is also preferable that the molecular weight is less than half of the molecular weight corresponding to the peak top. As a result, the same effect as when the weight average molecular weight of the low molecular weight resin is half or less of the weight average molecular weight of the high molecular weight resin can be obtained.
  • the water-soluble resin having the above molecular weight distribution can be obtained, for example, by mixing the above high molecular weight resin and the above low molecular weight resin.
  • two sets of peak tops are selected from those peak tops, and for at least one set of peak tops, the molecular weight corresponding to one peak top is determined. It may be less than half the molecular weight corresponding to the other peak top.
  • the larger of the molecular weights corresponding to the peak top is preferably 20,000 or more, and preferably 45,000 or more. Further, the one having the larger peak top molecular weight is preferably 2,000,000 or less, and may be 1,500,000 or less.
  • the upper limit of the molecular weight ratio is more preferably 0.3 or less, and further preferably 0.2 or less.
  • the lower limit of the molecular weight ratio is not particularly limited, but is preferably 0.001 or more, and may be 0.01 or more.
  • the difference between the weight average molecular weight of the high molecular weight resin and the weight average molecular weight of the low molecular weight resin is when PVA is included as the high molecular weight resin. It is preferably 10,000 to 80,000, more preferably 20,000 to 60,000.
  • PVP is contained as the high molecular weight resin
  • the above difference is preferably 50,000 to 1,500,000, more preferably 100,000 to 1,200,000.
  • the high molecular weight resin contains a water-soluble polysaccharide
  • the above difference is preferably 50,000 to 1,500,000, more preferably 100,000 to 1,200,000.
  • the water-soluble resin preferably contains PVA having a weight average molecular weight of 20,000 or more as the high molecular weight resin.
  • the weight average molecular weight is more preferably 30,000 or more, and further preferably 40,000 or more.
  • the water-soluble resin preferably contains PVP having a weight average molecular weight of 300,000 or more as the high molecular weight resin.
  • the weight average molecular weight is more preferably 400,000 or more, and further preferably 500,000 or more.
  • the water-soluble resin preferably contains a water-soluble polysaccharide having a weight average molecular weight of 300,000 or more as the high molecular weight resin. In this case, the weight average molecular weight is more preferably 400,000 or more, and further preferably 500,000 or more.
  • Preferred combinations of high molecular weight resin and low molecular weight resin are as follows, for example.
  • the water-soluble resin may satisfy only one requirement of the following combination, but may also satisfy the requirements of two or more combinations at the same time.
  • PVP high molecular weight resin
  • PVP low molecular weight resin having an Mw of 30,000 to 600,000.
  • the content of the high molecular weight resin is preferably 50% by mass or less with respect to the total water-soluble resin.
  • the upper limit of this numerical range is more preferably 40% by mass or less, and further preferably 30% by mass or less. Further, the lower limit of this numerical value range is more preferably 5% by mass or more, and further preferably 10% by mass or more.
  • the water-soluble resin may be in a form that does not substantially contain the low molecular weight resin.
  • substantially free of low molecular weight resin means that the content of the low molecular weight resin is 3% by mass or less with respect to the total water-soluble resin. In this embodiment, the content of the low molecular weight resin is preferably 1% by mass or less based on the total water-soluble resin.
  • the content of the polymer compound in the protective layer may be appropriately adjusted as necessary, but is preferably 20% by mass or more, more preferably 50% by mass or more, based on the total mass of the protective layer. , 70% by mass or more is more preferable.
  • the upper limit of the content is preferably 100% by mass or less, more preferably 99% by mass or less, and further preferably 98% by mass or less.
  • the protective layer may contain only one type of polymer compound, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
  • the protective layer preferably contains a surfactant containing an acetylene group. It is considered that the inclusion of the surfactant containing an acetylene group in the protective layer suppresses the adsorption of the polymer compound to the organic layer and is effective in removing the residue of the protective layer after removal with the removing liquid. Further, the protective layer contains a surfactant containing an acetylene group, and the removing liquid contains a surfactant for a removing liquid having an HLB value of 16.0 or less (more preferable range is as described above). This is further effective in removing the residue of the protective layer.
  • the number of acetylene groups in the molecule in the surfactant containing an acetylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and 1 to 2. Is more preferable.
  • the molecular weight of the surfactant containing an acetylene group is preferably relatively small, preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less. There is no particular lower limit, but it is preferably 200 or more.
  • the surfactant containing an acetylene group is preferably a compound represented by the following formula (9).
  • R 91 and R 92 are independently an alkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, or an aromatic heterocyclic group having 4 to 15 carbon atoms. ..
  • the number of carbon atoms of the aromatic heterocyclic group is preferably 1 to 12, more preferably 2 to 6, and even more preferably 2 to 4.
  • the aromatic heterocycle is preferably a 5-membered ring or a 6-membered ring.
  • the hetero atom contained in the aromatic heterocycle is preferably a nitrogen atom, an oxygen atom, or a sulfur atom.
  • R 91 and R 92 may each independently have a substituent, and examples of the substituent include the above-mentioned substituent T.
  • R 93 to R 96 are each independently a hydrocarbon group having 1 to 24 carbon atoms, n9 is an integer of 1 to 6, m9 is an integer twice n9, and n10 is an integer of 1 to 6. It is an integer, m10 is an integer twice n10, and l9 and l10 are independently numbers of 0 or more and 12 or less.
  • R 93 to R 96 are hydrocarbon groups, among which alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) and alkenyl groups (2 to 12 carbon atoms are preferable).
  • 2 to 6 is more preferable, 2 to 3 is more preferable), an alkynyl group (2 to 12 carbon atoms is preferable, 2 to 6 is more preferable, 2 to 3 is more preferable), and an aryl group (6 to 6 carbon atoms is more preferable).
  • 22 is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), and an arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable, and 7 to 11 is further preferable).
  • the alkyl group, alkenyl group, and alkynyl group may be linear or cyclic, and may be linear or branched.
  • R 93 to R 96 may have a substituent T as long as the effects of the present invention are exhibited. Further, R 93 to R 96 may be bonded to each other or form a ring via the above-mentioned connecting group L. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the hydrocarbon group in the formula with or without the linking group L below to form a ring.
  • R 93 and R 94 are preferably alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms). Of these, a methyl group is preferable.
  • R 95 and R 96 are preferably alkyl groups (preferably 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 3 to 6 carbon atoms). Of these, ⁇ (C n11 R 98 m11 ) -R 97 is preferable. R 95 and R 96 are particularly preferably isobutyl groups. n11 is an integer of 1 to 6, and an integer of 1 to 3 is preferable. m11 is twice the number of n11. R 97 and R 98 are each independently preferably a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms).
  • n9 is an integer of 1 to 6, and an integer of 1 to 3 is preferable.
  • m9 is an integer that is twice n9.
  • n10 is an integer of 1 to 6, and an integer of 1 to 3 is preferable.
  • m10 is an integer that is twice n10.
  • l9 and l10 are independently numbers from 0 to 12. However, l9 + l10 is preferably a number of 0 to 12, more preferably a number of 0 to 8, more preferably a number of 0 to 6, further preferably a number of more than 0 and less than 6, and more than 0. A number of 3 or less is even more preferable.
  • the compound of the formula (91) may be a mixture of compounds having different numbers, and in that case, the numbers of l9 and l10, or l9 + l10 are the numbers including the decimal point. You may.
  • R 93 , R 94 , and R 97 to R 100 are each independently a hydrocarbon group having 1 to 24 carbon atoms, and l11 and l12 are independently numbers of 0 or more and 12 or less.
  • R 93 , R 94 , and R 97 to R 100 are alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) and alkenyl groups (preferably 2 to 12 carbon atoms).
  • alkyl group, alkenyl group, and alkynyl group may be chain or cyclic, and may be linear or branched.
  • R 93 , R 94 , and R 97 to R 100 may have a substituent T as long as the effects of the present invention are exhibited. Further, R 93 , R 94 , and R 97 to R 100 may be bonded to each other or form a ring via a connecting group L. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the hydrocarbon group in the formula with or without the linking group L to form a ring.
  • R 93 , R 94 , and R 97 to R 100 are each independently preferably an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms).
  • a methyl group is preferable.
  • the number of l11 + l12 is preferably 0 to 12, more preferably 0 to 8, more preferably 0 to 6, more preferably more than 0 and less than 6, more preferably more than 0 and 5 or less.
  • the number of is even more preferable, the number of more than 0 and less than 4 is even more preferable, the number of more than 0 and less than 3 or more than 0 and less than or equal to 1.
  • l11 and l12 may be a mixture of compounds having different numbers in the compound of the formula (92), and in that case, the numbers of l11 and l12, or l11 + l12 are the numbers including the decimal point. May be good.
  • Surfactants containing an acetylene group include Surfynol 104 series (trade name, Nisshin Kagaku Kogyo Co., Ltd.), Acetyrenol E00, E40, E13T, and 60 (all trade names, rivers). (Manufactured by Ken Fineke Chemical Co., Ltd.), among which Surfinol 104 series, acetylenol E00, E40 and E13T are preferable, and acetylenol E40 and E13T are more preferable.
  • the Surfinol 104 series and acetylenol E00 are surfactants having the same structure.
  • the protective layer may contain other surfactants other than the above-mentioned surfactant containing an acetylene group for the purpose of improving the coatability of the protective layer forming composition described later.
  • the other surfactant may be any other surfactant, such as nonionic surfactant, anionic surfactant, and amphoteric fluorine surfactant, as long as it lowers the surface tension.
  • examples of other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, and polyoxyethylene stearyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene nonylphenyl ether.
  • Polyoxyethylene alkylaryl ethers such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan triole
  • Nonionic surfactants such as sorbitan alkyl esters such as ate, monoglyceride alkyl esters such as glycerol monostearate and glycerol monooleate, oligomers containing fluorine or silicon; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate.
  • Alkylnaphthalene sulfonates such as sodium butylnaphthalene sulfonate, sodium pentylnaphthalene sulfonate, sodium hexylnaphthalene sulfonate, sodium octylnaphthalene sulfonate, alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonic acid such as sodium dodecyl sulfonate
  • Anionic surfactants such as salts and sulfosuccinate salts such as sodium dilauryl sulfosuccinate; and amphoteric surfactants such as alkyl betaines such as lauryl betaine and stearyl betaine, and amino acids can be used.
  • the total amount of the surfactant containing the acetylene group and the other surfactant is the total amount of the surfactant added. It is preferably 0.05 to 20% by mass, more preferably 0.07 to 15% by mass, and further preferably 0.1 to 10% by mass with respect to the total mass of the protective layer.
  • These surfactants may be used alone or in combination of two or more. When a plurality of items are used, the total amount is within the above range. Further, in the present invention, the structure may be substantially free of other surfactants.
  • substantially free means that the content of the other surfactant is 5% by mass or less of the content of the surfactant containing an acetylene group, preferably 3% by mass or less, and 1% by mass or less. Is more preferable.
  • the surface tension of the 0.1% by mass aqueous solution of another surfactant at 23 ° C. is preferably 45 mN / m or less, more preferably 40 mN / m or less, and more preferably 35 mN / m or less. More preferred. As the lower limit, it is preferably 5 mN / m or more, more preferably 10 mN / m or more, and further preferably 15 mN / m or more.
  • the surface tension of the surfactant may be appropriately selected depending on the type of other surfactant to be selected.
  • the protective layer contains an antiseptic or antifungal agent.
  • the preservative and antifungal agent (hereinafter, preservative and the like) preferably contain at least one additive having an antibacterial or antifungal action and selected from water-soluble or water-dispersible organic compounds. ..
  • the additive having an antibacterial or antifungal action such as an antiseptic include an organic antibacterial agent or an antifungal agent, an inorganic antibacterial agent or an antifungal agent, a natural antibacterial agent or an antifungal agent and the like.
  • antibacterial or antifungal agent those described in "Antibacterial / Antifungal Technology" published by Toray Research Center Co., Ltd. can be used.
  • the effect of suppressing the increase of coating defects due to the growth of bacteria inside the solution after long-term storage at room temperature is more effectively exhibited.
  • preservatives include phenol ether compounds, imidazole compounds, sulfone compounds, N. haloalkylthio compounds, anilide compounds, pyrrol compounds, quaternary ammonium salts, alcine compounds, pyridine compounds, and triazine compounds. , Benzoisothiazolin-based compounds, isothiazoline-based compounds and the like. Specifically, for example, 2 (4 thiocyanomethyl) benzimidazolone, 1,2 benzothiazolone, 1,2-benzisothiazolin-3-one, N-fluorodichloromethylthio-phthalimide, 2,3,5,6-tetrachloro.
  • chitosan a basic polysaccharide obtained by hydrolyzing chitin contained in the crustacean of crab or shrimp.
  • the content of the preservative or the like in the protective layer is preferably 0.005 to 5% by mass, more preferably 0.01 to 3% by mass, and 0.05 to 0.05 to the total mass of the protective layer. It is more preferably 2% by mass, and even more preferably 0.1 to 1% by mass.
  • the preservative or the like one kind or a plurality of preservatives may be used. When a plurality of items are used, the total amount is within the above range.
  • the antibacterial effect of preservatives and the like can be evaluated in accordance with JIS Z 2801 (antibacterial processed product-antibacterial test method / antibacterial effect). In addition, the antifungal effect can be evaluated in accordance with JIS Z 2911 (mold resistance test).
  • the protective layer may contain a light shielding agent.
  • a light-shielding agent By blending a light-shielding agent, the influence of light damage to the organic layer and the like can be further suppressed.
  • the light-shielding agent for example, a known colorant or the like can be used, and examples thereof include organic or inorganic pigments or dyes, preferably inorganic pigments, and more preferably carbon black, titanium oxide, titanium nitride and the like. ..
  • the content of the light-shielding agent is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and further preferably 5 to 25% by mass with respect to the total mass of the protective layer.
  • the light-shielding agent one type or a plurality of types may be used. When a plurality of items are used, the total amount is within the above range.
  • composition for forming a protective layer is a composition used for forming a protective layer contained in the laminate used in the present invention.
  • the composition for forming a protective layer preferably contains a polymer compound.
  • the composition for forming a protective layer may contain the above-mentioned surfactant containing an acetylene group, other surfactants, preservatives, antifungal agents and light-shielding agents.
  • the composition for forming a protective layer preferably contains a water-soluble resin and a surfactant.
  • the surfactant may be the above-mentioned surfactant containing an acetylene group or the above-mentioned other surfactant, but a surfactant containing an acetylene group is preferable.
  • the content of the components contained in the protective layer forming composition the content of each component with respect to the total mass of the protective layer may be read as the content with respect to the solid content of the protective layer forming composition. preferable.
  • the composition for forming a protective layer preferably contains a solvent described later.
  • the protective layer can be formed, for example, by applying the protective layer forming composition onto the organic layer and drying it.
  • a method of applying the composition for forming a protective layer coating is preferable.
  • application methods include slit coating method, casting method, blade coating method, wire bar coating method, spray coating method, dipping coating method, bead coating method, air knife coating method, curtain coating method, inkjet method, etc.
  • spin coat method and the Langmuir-Blodgett (LB) method. It is more preferable to use the casting method, the spin coating method, and the inkjet method.
  • LB Langmuir-Blodgett
  • the protective layer forming composition can also be formed by a method of transferring a coating film previously formed on a temporary support by the above-mentioned applying method or the like onto an application target (for example, an organic layer).
  • an application target for example, an organic layer.
  • the description of paragraphs 0023, 0036 to 0051 of JP-A-2006-023696, paragraphs 096 to 0108 of JP-A-2006-047592, and the like can be referred to.
  • the solvent contained in the composition for forming a protective layer examples include the above-mentioned aqueous solvent, and water or a mixture of water and a water-soluble solvent is preferable, and water is more preferable.
  • the aqueous solvent is a mixed solvent, it is preferably a mixed solvent of an organic solvent having a solubility in water at 23 ° C. of 1 g or more and water.
  • the solubility of the organic solvent in water at 23 ° C. is more preferably 10 g or more, further preferably 30 g or more.
  • a fluorine-based solvent can also be used as the solvent.
  • the fluorine-based solvent is an organic solvent containing a fluorine atom.
  • the fluorine atom content in the fluorine-based solvent used in the present invention is preferably 10 to 80%, more preferably 15 to 75%, and even more preferably 20 to 70%.
  • the fluorine atom content here is represented by (the number of fluorine atoms constituting the fluorine-based solvent / the number of all atoms constituting the fluorine solvent) ⁇ 100 (%).
  • the boiling point of the fluorine-based solvent used in the present invention is 101325 Pa, preferably 40 to 250 ° C., more preferably 50 to 200 ° C., and even more preferably 55 to 180 ° C.
  • the fluorine-based solvent is preferably an alcohol, and more preferably an alcohol composed of an alkyl group and an OH group substituted with at least one fluorine atom.
  • alcohol a resin having polarity and not containing a fluorine atom such as resin A1 can be easily dissolved.
  • the number of carbon atoms of the alkyl group substituted with at least one fluorine atom is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 10.
  • the number of fluorine atoms in the alkyl group substituted with at least one fluorine atom is preferably 1 to 30, more preferably 3 to 20, and even more preferably 4 to 12.
  • fluorine-based solvent examples include 2,2,3,3-tetrafluoro-1-propanol, 2,2,3,3,4,5,5-octafluoro-1-pentanol, 2, 2,3,3,3-pentafluoro-1-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,4,5,4-heptafluoro- Examples thereof include 1-butanol, 1H, 1H, 7H-dodecafluoro-1-heptanol, nonafluorobutyl ethyl ether, perfluorotributylamine and the like.
  • the solid content concentration of the protective layer forming composition is preferably 0.5 to 30% by mass from the viewpoint of being more uniform in thickness when the protective layer forming composition is applied and being easy to apply. It is more preferably 0 to 20% by mass, and even more preferably 2.0 to 14% by mass.
  • the laminate used in the present invention includes a photosensitive layer.
  • the photosensitive layer is a layer used for development using a developing solution.
  • the development is preferably a negative type development.
  • a known photosensitive layer for example, a photoresist layer
  • the photosensitive layer may be a negative type photosensitive layer or a positive type photosensitive layer.
  • the exposed portion of the photosensitive layer is sparingly soluble in a developing solution containing an organic solvent.
  • the poorly soluble means that the exposed portion is difficult to dissolve in the developing solution.
  • the dissolution rate of the photosensitive layer in the exposed portion in the developing solution is smaller (difficult to dissolve) than the dissolution rate of the photosensitive layer in the developing solution in the unexposed portion.
  • the polarity is changed by exposing light having at least one wavelength having a wavelength of 365 nm (i line), a wavelength of 248 nm (KrF line) and a wavelength of 193 nm (ArF line) at an irradiation amount of 50 mJ / cm 2 or more.
  • Sp value is preferably less than 19.0 (MPa) 1/2, and less than 18.5 (MPa) 1/2 or less. It is more preferable that the solvent is poorly soluble in a solvent of 18.0 (MPa) 1/2 or less.
  • the solubility parameter (sp value) is a value [unit: (MPa) 1/2 ] obtained by the Okitsu method.
  • the Okitsu method is one of the well-known methods for calculating the sp value. For example, Vol. 29, No. 6 (1993) The method described in detail on pages 249-259.
  • the polarity can be changed as described above. It is more preferable to change.
  • the photosensitive layer preferably has a photosensitivity to i-ray irradiation.
  • the photosensitivity means that the dissolution rate in an organic solvent (preferably butyl acetate) is changed by irradiation with at least one of active rays and radiation (irradiation with i-rays if the photosensitivity is with respect to i-ray irradiation). To do.
  • the photosensitive layer examples include a photosensitive layer containing a resin whose dissolution rate in a developing solution changes due to the action of an acid (hereinafter, also referred to as "specific resin for a photosensitive layer").
  • the change in the dissolution rate in the specific resin for the photosensitive layer is preferably a decrease in the dissolution rate.
  • the dissolution rate of the specific resin for the photosensitive layer in an organic solvent having an sp value of 18.0 (MPa) 1/2 or less before the dissolution rate changes is more preferably 40 nm / sec or more.
  • the dissolution rate of the specific resin for the photosensitive layer in an organic solvent having an sp value of 18.0 (MPa) 1/2 or less after the dissolution rate is changed is more preferably less than 1 nm / sec.
  • the specific resin for the photosensitive layer is also soluble in an organic solvent having an sp value (solubility parameter) of 18.0 (MPa) 1/2 or less and the dissolution rate changes before the dissolution rate changes. After that, it is preferable that the resin is sparingly soluble in an organic solvent having an sp value of 18.0 (MPa) 1/2 or less.
  • "soluble in an organic solvent having an sp value (solubility parameter) of 18.0 (MPa) 1/2 or less” means that a solution of a compound (resin) is applied onto a substrate and at 100 ° C. for 1 minute.
  • the dissolution rate of a coating film (thickness 1 ⁇ m) of a compound (resin) formed by heating when immersed in a developing solution at 23 ° C. is 20 nm / sec or more, which means that the “sp value”. Is sparingly soluble in an organic solvent of 18.0 (MPa) 1/2 or less "means a compound (resin) formed by applying a solution of a compound (resin) on a substrate and heating at 100 ° C. for 1 minute. ), The dissolution rate of the coating film (thickness 1 ⁇ m) in the developing solution at 23 ° C. is less than 10 nm / sec.
  • the photosensitive layer examples include a photosensitive layer containing a specific resin for a photosensitive layer and a photoacid generator, a photosensitive layer containing a polymerizable compound, a photopolymerization initiator, and the like. Further, the photosensitive layer is preferably a chemically amplified photosensitive layer from the viewpoint of achieving both high storage stability and fine pattern formation.
  • the photosensitive layer containing the specific resin for the photosensitive layer and the photoacid generator will be described.
  • the photosensitive layer in the present invention preferably contains a specific resin for the photosensitive layer.
  • the specific resin for the photosensitive layer is preferably an acrylic polymer.
  • the "acrylic polymer” is an addition polymerization type resin, a polymer containing a repeating unit derived from (meth) acrylic acid or an ester thereof, and other than the repeating unit derived from (meth) acrylic acid or an ester thereof.
  • the repeating unit of the above for example, a repeating unit derived from styrenes, a repeating unit derived from a vinyl compound, and the like may be included.
  • the acrylic polymer preferably contains 50 mol% or more, more preferably 80 mol% or more, of repeating units derived from (meth) acrylic acid or an ester thereof, based on all the repeating units in the polymer. It is particularly preferable that the polymer consists only of repeating units derived from (meth) acrylic acid or an ester thereof.
  • a resin having a repeating unit having a structure in which an acid group is protected by an acid-decomposable group is preferably mentioned.
  • the structure in which the acid group is protected by the acid-degradable group include a structure in which the carboxy group is protected by the acid-degradable group, a structure in which the phenolic hydroxy group is protected by the acid-degradable group, and the like.
  • the repeating unit having a structure in which the acid group is protected by an acid-degradable group a repeating unit having a structure in which the carboxy group in the monomer unit derived from (meth) acrylic acid is protected by an acid-degradable group, p.
  • Examples thereof include a repeating unit having a structure in which a phenolic hydroxy group in a monomer unit derived from hydroxystyrenes such as -hydroxystyrene and ⁇ -methyl-p-hydroxystyrene is protected by an acid-degradable group.
  • Examples of the repeating unit having a structure in which the acid group is protected by an acid-degradable group include a repeating unit containing an acetal structure, and a repeating unit containing a cyclic ether ester structure in the side chain is preferable.
  • the cyclic ether ester structure it is preferable that the oxygen atom in the cyclic ether structure and the oxygen atom in the ester bond are bonded to the same carbon atom to form an acetal structure.
  • the repeating unit represented by the following formula (1) is preferable.
  • the “repetition unit represented by the equation (1)” and the like are also referred to as the “repetition unit (1)” and the like.
  • R 8 represents a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms)
  • L 1 represents a carbonyl group or a phenylene group.
  • R 1 to R 7 independently represent a hydrogen atom or an alkyl group.
  • R 8 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
  • L 1 represents a carbonyl group or a phenylene group, and is preferably a carbonyl group.
  • R 1 to R 7 independently represent a hydrogen atom or an alkyl group. The alkyl groups in R 1 to R 7 are synonymous with R 8 and the preferred embodiments are the same. Further, among the R 1 ⁇ R 7, preferably more than one is a hydrogen atom, it is more preferable that all of R 1 ⁇ R 7 are hydrogen atoms.
  • repeating unit (1) a repeating unit represented by the following formula (1-A) or a repeating unit represented by the following formula (1-B) is preferable.
  • the radically polymerizable monomer used for forming the repeating unit (1) a commercially available one may be used, or one synthesized by a known method may be used. For example, it can be synthesized by reacting (meth) acrylic acid with a dihydrofuran compound in the presence of an acid catalyst. Alternatively, it can also be formed by reacting a carboxy group or a phenolic hydroxy group with a dihydrofuran compound after polymerization with a precursor monomer.
  • a repeating unit represented by the following formula (2) is also preferably mentioned.
  • A represents a group eliminated by the action of a hydrogen atom or an acid.
  • Examples of the group desorbed by the action of the acid include an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) and an alkoxyalkyl group (preferably 2 to 12 carbon atoms).
  • R 10 represents a substituent, and an example of the substituent T can be given.
  • R 9 represents a group synonymous with R 8 in the formula (1).
  • nx represents an integer of 0 to 3.
  • repeating unit (2) Specific examples of the repeating unit (2) are shown below, but the present invention is not construed as being limited thereto.
  • the content of the repeating unit (preferably the repeating unit (1) or the repeating unit (2)) having a structure in which the acid group is protected by the acid-degradable group contained in the specific resin for the photosensitive layer is 5 to 80 mol. % Is preferred, 10-70 mol% is more preferred, and 10-60 mol% is even more preferred.
  • the acrylic polymer may contain only one type of repeating unit (1) or repeating unit (2), or may contain two or more types. When two or more types are used, the total amount is preferably in the above range.
  • the specific resin for the photosensitive layer may contain a repeating unit containing a crosslinkable group.
  • the specific resin for the photosensitive layer preferably contains a repeating unit (repeating unit (3)) containing a crosslinkable group, but preferably has a configuration that does not substantially contain the repeating unit (3) containing a crosslinkable group. .. With such a configuration, the photosensitive layer can be removed more effectively after patterning.
  • substantially not contained means, for example, 3 mol% or less, preferably 1 mol% or less, of all the repeating units of the specific resin for the photosensitive layer.
  • the specific resin for the photosensitive layer may contain other repeating units (repeating units (4)).
  • the radically polymerizable monomer used for forming the repeating unit (4) include the compounds described in paragraphs 0021 to 0024 of JP2004-246623A.
  • a preferred example of the repeating unit (4) is a repeating derived from at least one selected from the group consisting of a hydroxy group-containing unsaturated carboxylic acid ester, an alicyclic structure-containing unsaturated carboxylic acid ester, styrene, and an N-substituted maleimide. The unit is mentioned.
  • benzyl (meth) acrylate, tricyclo (meth) acrylate [5.2.1.0 2,6 ] decane-8-yl, tricyclo (meth) acrylate [5.2.1.0 2,] 6 ] (Meta) acrylic acid esters containing alicyclic structure such as decane-8-yloxyethyl, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, or Hydrophobic monomers such as styrene are preferred.
  • the repeating unit (4) may be used alone or in combination of two or more.
  • the content of the monomer unit forming the repeating unit (4) when the repeating unit (4) is contained is preferably 1 to 60 mol%, preferably 5 to 50 mol%. % Is more preferred, and 5-40 mol% is even more preferred. When two or more types are used, the total amount is preferably in the above range.
  • a radically polymerizable unit used to form at least a repeating unit (1), a repeating unit (2), or the like. It can be synthesized by polymerizing a radically polymerizable monomer mixture containing a body in an organic solvent using a radical polymerization initiator.
  • a specific resin for the photosensitive layer 2,3-dihydrofuran is added to an acid anhydride group in a precursor copolymer copolymerized with unsaturated polyvalent carboxylic acid anhydrides at room temperature in the absence of an acid catalyst.
  • a copolymer obtained by addition at a temperature of about (25 ° C.) to 100 ° C. is also preferable.
  • BzMA / THFMA / t-BuMA (molar ratio: 20-60: 35-65: 5-30)
  • BzMA / THFAA / t-BuMA (molar ratio: 20-60: 35-65: 5-30)
  • BzMA / THPMA / t-BuMA (molar ratio: 20-60: 35-65: 5-30)
  • BzMA / PEES / t-BuMA (molar ratio: 20-60: 35-65: 5-30)
  • BzMA is benzyl methacrylate
  • THFMA is tetrahydrofuran-2-yl methacrylate
  • t-BuMA is t-butyl methacrylate
  • THFAA is tetrahydrofuran-2-yl acrylate
  • THPMA is tetrahydro-2H.
  • PEES is p-ethoxyethoxysty
  • the content of the specific resin for the photosensitive layer is preferably 20 to 99% by mass and 40 to 99% by mass with respect to the total mass of the photosensitive layer. Is more preferable, and 70 to 99% by mass is further preferable.
  • the specific resin for the photosensitive layer may contain only one type, or may contain two or more types. When two or more types are used, the total amount is preferably in the above range.
  • the content of the specific resin for the photosensitive layer is preferably 10% by mass or more, more preferably 50% by mass or more, and 90% by mass or more, based on the total mass of the resin components contained in the photosensitive layer. Is more preferable.
  • the weight average molecular weight of the specific resin for the photosensitive layer is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 35,000 or more.
  • the upper limit value is not particularly specified, but is preferably 100,000 or less, and may be 70,000 or less, or 50,000 or less.
  • the amount of the component having a weight average molecular weight of 1,000 or less contained in the specific resin for the photosensitive layer is preferably 10% by mass or less, preferably 5% by mass or less, based on the total mass of the specific resin for the photosensitive layer. Is more preferable.
  • the molecular weight dispersion (weight average molecular weight / number average molecular weight) of the specific resin for the photosensitive layer is preferably 1.0 to 4.0, more preferably 1.1 to 2.5.
  • the photosensitive layer preferably further contains a photoacid generator.
  • the photoacid generator is preferably a photoacid generator that decomposes by 80 mol% or more when the photosensitive layer is exposed to an exposure amount of 100 mJ / cm 2 at a wavelength of 365 nm.
  • the degree of decomposition of the photoacid generator can be determined by the following method. Details of the following composition for forming a photosensitive layer will be described later.
  • a photosensitive layer is formed on a silicon wafer substrate using a composition for forming a photosensitive layer, heated at 100 ° C. for 1 minute, and after heating, the photosensitive layer is exposed to 100 mJ / cm 2 using light having a wavelength of 365 nm. To expose.
  • the thickness of the photosensitive layer after heating is 700 nm.
  • THF methanol / tetrahydrofuran
  • the extract extracted into the solution is analyzed by HPLC (high performance liquid chromatography) to calculate the decomposition rate of the photoacid generator from the following formula.
  • Decomposition rate (%) decomposition product amount (mol) / amount of photoacid generator contained in the photosensitive layer before exposure (mol) x 100
  • the photoacid generator preferably decomposes by 85 mol% or more when the photosensitive layer is exposed to an exposure amount of 100 mJ / cm 2 at a wavelength of 365 nm.
  • the photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as “oxime sulfonate compound”).
  • the oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-) It is preferably an oxime sulfonate compound represented by 105).
  • OS-1 X 3 is an alkyl group, an alkoxyl group, or a halogen atom.
  • Alkyl group and an alkoxyl group represented by X 3 may have a substituent.
  • the halogen atom in the X 3, a chlorine atom or a fluorine atom is preferable.
  • m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X 3 may be the same or different.
  • R 34 represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxyl group of numbers 1 to 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W or an anthranyl group optionally substituted with W.
  • W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxyl halide having 1 to 5 carbon atoms. It represents a group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.
  • m3 is a 3
  • X 3 is a methyl group
  • the substitution position of X 3 is ortho
  • R thirty-four a linear alkyl group having 1 to 10 carbon atoms
  • a compound having a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group is particularly preferable.
  • R s1 represents an alkyl group, an aryl group, or a heteroaryl group
  • ns represents 1 or 2
  • ms represents an integer from 0 to 6.
  • an alkyl group represented by R s1 preferably having 1 to 30 carbon atoms
  • an aryl group preferably having 6 to 30 carbon atoms
  • a heteroaryl group may have a substituent T.
  • R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms). , Hydrogen atom or alkyl group is more preferable.
  • R s2 that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.
  • the alkyl group or aryl group represented by R s2 may have a substituent T.
  • Xs represents O or S, and is preferably O.
  • the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
  • ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
  • the alkyl group represented by R s6 preferably having 1 to 30 carbon atoms
  • the alkyloxy group preferably having 1 to 30 carbon atoms
  • ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.
  • the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111).
  • the compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS-105). -108) or a compound represented by the formula (OS-109) is particularly preferable.
  • R t1 represents an alkyl group, an aryl group or a heteroaryl group
  • R t7 represents a hydrogen atom or a bromine atom
  • R t8 represents a hydrogen atom and the number of carbon atoms.
  • R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
  • R t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, or a phenyl group.
  • it represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms.
  • R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
  • R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
  • the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
  • oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692A and paragraphs of JP2015-194674A.
  • the compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.
  • oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
  • Ru9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Represents an aryl group or a heteroaryl group.
  • R u9 is a cyano group or an aryl group
  • Ru2a represents an alkyl or aryl group
  • Xu is -O-, -S-, -NH- , -NR u5-, -CH 2- , -CR u6 H- or CR u6 R u7. Represents ⁇ , and R u5 to R u7 independently represent an alkyl group or an aryl group.
  • Ru1 to Ru4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxyl group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group. 2 in turn, each may be bonded to each other to form a ring of the R u1 ⁇ R u4. At this time, the ring may be condensed to form a fused ring together with the benzene ring.
  • All of Ru1 to Ru4 are hydrogen atoms.
  • Any of the above-mentioned substituents may further have a substituent.
  • the compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
  • the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
  • Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraph numbers 0102 to 0106 of JP2011-209692 and paragraph numbers 0195 to 0207 of JP2015-194674. These contents are incorporated herein by reference. Among the above compounds, b-9, b-16, b-31, and b-33 are preferable. Examples of commercially available products include WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Chemical Co., Ltd.), and the like. Can be done.
  • the photoacid generator that is sensitive to active light
  • those that do not contain 1,2-quinonediazide compounds are preferable.
  • the 1,2-quinonediazide compound produces a carboxy group by a sequential photochemical reaction, but its quantum yield is 1 or less, which is lower in sensitivity than the oxime sulfonate compound.
  • the oxime sulfonate compound acts as a catalyst for the deprotection of the protected acid group by the acid generated in response to the active light, so that a large number of acids are produced by the action of one photon.
  • the quantum yield exceeds 1, and becomes a large value such as a power of 10, and it is presumed that high sensitivity can be obtained as a result of so-called chemical amplification.
  • the oxime sulfonate compound has a broad ⁇ -conjugated system, it has absorption even on the long wavelength side, and not only far ultraviolet rays (DUV), ArF rays, KrF rays, and i rays, but also It also shows very high sensitivity in the g-line.
  • the acid-decomposable group By using a tetrahydrofuranyl group as the acid-decomposable group in the photosensitive layer, it is possible to obtain acid-decomposability equal to or higher than that of acetal or ketal. As a result, the acid-degradable group can be reliably consumed by post-baking in a shorter time. Further, by using the oxime sulfonate compound which is a photoacid generator in combination, the sulfonic acid generation rate is increased, so that the acid production is promoted and the decomposition of the acid-degradable group of the resin is promoted. Further, since the acid obtained by decomposing the oxime sulfonate compound is a sulfonic acid having a small molecule, it has high diffusibility in the cured membrane and can be made more sensitive.
  • the photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, and 0.5 to 10% by mass with respect to the total mass of the photosensitive layer. It is more preferable to use 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass.
  • the photoacid generator one type may be used alone, or two or more types may be used in combination. When two or more types are used, the total amount is preferably in the above range.
  • the photosensitive layer preferably contains a basic compound from the viewpoint of liquid storage stability of the composition for forming a photosensitive layer, which will be described later.
  • a basic compound from the viewpoint of liquid storage stability of the composition for forming a photosensitive layer, which will be described later.
  • the basic compound it can be arbitrarily selected and used from those used in known chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.
  • Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
  • Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
  • heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, and the like.
  • Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
  • Examples of the quaternary ammonium salt of the carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
  • the content of the basic compound is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the specific resin for the photosensitive layer, and 0.002 to 0. More preferably, it is 5 parts by mass.
  • the basic compound one type may be used alone or two or more types may be used in combination, but it is preferable to use two or more types in combination, more preferably two types in combination, and a heterocyclic amine. It is more preferable to use two kinds in combination. When two or more types are used, the total amount is preferably in the above range.
  • the photosensitive layer preferably contains a surfactant from the viewpoint of improving the coatability of the composition for forming a photosensitive layer, which will be described later.
  • a surfactant any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but the preferred surfactant is a nonionic surfactant.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, polyoxyethylene glycol higher fatty acid diesters, fluorine-based and silicone-based surfactants. .. It is more preferable that the surfactant contains a fluorine-based surfactant or a silicone-based surfactant.
  • fluorine-based surfactants or silicone-based surfactants examples include JP-A-62-0366663, JP-A-61-226746, JP-A-61-226745, and JP-A-62-170950. , JP-A-63-034540, JP-A-07-230165, JP-A-08-062834, JP-A09-054432, JP-A09-005988, JP-A-2001-330953. Activators can be mentioned, and commercially available surfactants can also be used.
  • surfactants that can be used, for example, Ftop EF301, EF303 (above, manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (above, manufactured by Sumitomo 3M Co., Ltd.), Megafuck F171, F173, F176. , F189, R08 (above, manufactured by DIC Co., Ltd.), Surfron S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by AGC Seimi Chemical Co., Ltd.), PolyFox series such as PF-6320 ( Fluorine-based surfactants such as OMNOVA) or silicone-based surfactants can be mentioned. Further, the polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone-based surfactant.
  • a surfactant a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography when a repeating unit A and a repeating unit B represented by the following formula (41) is contained and tetrahydrofuran (THF) is used as a solvent.
  • a copolymer having (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferable example.
  • R 41 and R 43 independently represent a hydrogen atom or a methyl group
  • R 42 represents a linear alkylene group having 1 to 4 carbon atoms
  • R 44 represents a hydrogen atom or 1 carbon atom.
  • L 4 represents an alkyl group
  • L 4 represents an alkylene group having 3 to 6 carbon atoms
  • p4 and q4 is the mass percentage representing the polymerization ratio
  • p4 is a number from 10% by weight to 80% by weight Represented
  • q4 represents a numerical value of 20% by mass or more and 90% by mass or less
  • r4 represents an integer of 1 or more and 18 or less
  • n4 represents an integer of 1 or more and 10 or less.
  • L 4 is preferably a branched alkylene group represented by the following formula (42).
  • R 45 in the formula (42) represents an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl having 2 or 3 carbon atoms is preferable in terms of wettability to the surface to be coated. Groups are more preferred.
  • -CH 2- CH (R 45 )-(42) The weight average molecular weight of the copolymer is more preferably 1,500 or more and 5,000 or less.
  • the amount of the surfactant added is preferably 10 parts by mass or less, preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the specific resin for the photosensitive layer. Is more preferable, and 0.01 to 1 part by mass is further preferable.
  • the surfactant one type may be used alone, or two or more types may be mixed and used. When two or more types are used, the total amount is preferably in the above range.
  • the photosensitive layer contains an antioxidant, a plasticizer, a thermal radical generator, a thermoacid generator, an acid growth agent, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor.
  • an antioxidant e.g., a plasticizer, a thermal radical generator, a thermoacid generator, an acid growth agent, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor.
  • the thickness (thickness) of the photosensitive layer in the present invention is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, further preferably 0.75 ⁇ m or more, and particularly preferably 0.8 ⁇ m or more. ..
  • the upper limit of the thickness of the photosensitive layer is preferably 10 ⁇ m or less, more preferably 5.0 ⁇ m or less, and even more preferably 2.0 ⁇ m or less.
  • the total thickness of the photosensitive layer and the protective layer is preferably 0.2 ⁇ m or more, more preferably 1.0 ⁇ m or more, and further preferably 2.0 ⁇ m or more.
  • the upper limit value is preferably 20.0 ⁇ m or less, more preferably 10.0 ⁇ m or less, and further preferably 5.0 ⁇ m or less.
  • the photosensitive layer in the present invention is subjected to development using a developing solution.
  • a developing solution containing an organic solvent is preferable.
  • the content of the organic solvent with respect to the total mass of the developing solution is preferably 90 to 100% by mass, more preferably 95 to 100% by mass.
  • the developing solution may be a developing solution containing only an organic solvent. The method for developing the photosensitive layer using a developing solution will be described later.
  • -Organic solvent- Sp value of the organic solvent contained in the developer is preferably less than 19 MPa 1/2, and more preferably 18 MPa 1/2 or less.
  • the organic solvent contained in the developing solution include polar solvents such as ketone solvents, ester solvents and amide solvents, and hydrocarbon solvents.
  • the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methylamyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, and the like.
  • Examples thereof include methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
  • ester solvent examples include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl.
  • the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
  • hydrocarbon solvent examples include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
  • the organic solvent may be used alone or in combination of two or more. Further, it may be used by mixing with an organic solvent other than the above.
  • the content of water with respect to the total mass of the developing solution is preferably less than 10% by mass, and more preferably substantially no water.
  • substantially free of water as used herein means that, for example, the content of water with respect to the total mass of the developing solution is 3% by mass or less, more preferably not more than the measurement limit.
  • the amount of the organic solvent used with respect to the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less with respect to the total amount of the developing solution.
  • the organic developer preferably contains at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent and an amide solvent.
  • the organic developer may contain an appropriate amount of a basic compound, if necessary. Examples of the basic compound include those described in the above section of the basic compound.
  • the vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less at 23 ° C.
  • solvents having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, 2-heptanone (methylamylketone), 4-heptanone, 2-hexanone, and diisobutyl.
  • Ketone solvents such as ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylisobutylketone, butyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol Ester solvents such as monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl nitate, propyl silicate, ethyl lactate, butyl lactate, propyl lactate, etc.
  • Amido-based solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as octane and decane.
  • aromatic hydrocarbon solvents such as toluene and xylene
  • aliphatic hydrocarbon solvents such as octane and decane.
  • Specific examples of the solvent having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, 4-heptanone, 2-hexanone, diisobutylketone, cyclohexanone, and the like.
  • Ketone solvents such as methylcyclohexanone and phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, Ester solvents such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl Examples thereof include amide-based solvents such as formamide, aromatic hydrocarbon-based solvents such as xylene, and aliphatic hydrocarbon-based solvents such as octane and decane.
  • amide-based solvents such as formamide, aromatic hydrocarbon
  • the developer may contain a surfactant.
  • the surfactant is not particularly limited, but for example, the surfactant described in the above section of the protective layer is preferably used.
  • the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0, based on the total amount of the developing solution. It is 0.01 to 0.5% by mass.
  • composition for forming a photosensitive layer of the present invention is a composition used for forming a photosensitive layer contained in the laminate used in the present invention.
  • the photosensitive layer can be formed, for example, by applying a composition for forming a photosensitive layer onto a protective layer and drying it.
  • the application method for example, the description of the application method of the composition for forming a protective layer in the protective layer described above can be taken into consideration.
  • the composition for forming a photosensitive layer includes the above-mentioned components contained in the photosensitive layer (for example, a specific resin for a photosensitive layer, a photoacid generator, a basic compound, a surfactant, and other components), a solvent, and the like. Is preferably included.
  • the components contained in these photosensitive layers are preferably dissolved or dispersed in a solvent, and more preferably dissolved.
  • the content of the components contained in the composition for forming a photosensitive layer the content of each component with respect to the total mass of the photosensitive layer may be read as the content with respect to the solid content of the composition for forming a photosensitive layer. preferable.
  • organic solvent used in the composition for forming a photosensitive layer a known organic solvent can be used, and ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl.
  • Ethers propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers Examples thereof include acetates, esters, ketones, amides, lactones and the like.
  • Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;
  • Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether;
  • Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate;
  • Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;
  • the composition for forming the photosensitive layer contains an organic solvent
  • the content of the organic solvent is preferably 1 to 3,000 parts by mass per 100 parts by mass of the specific resin for the photosensitive layer, and is preferably 5 to 2,000 parts by mass. It is more preferably 10 to 1,500 parts by mass.
  • These organic solvents may be used alone or in admixture of two or more. When two or more types are used, the total amount is preferably in the above range.
  • the following steps (1) to (6) are a series of work steps related to patterning of the organic layer.
  • the method for producing the laminate includes at least the following step (1).
  • the method for patterning the organic layer includes at least the following step (5).
  • (6) A step of removing the protective layer using a removing liquid.
  • the method for patterning an organic layer of the present embodiment includes a step of forming a protective layer on the organic layer. Usually, this step is performed after forming an organic layer on the base material.
  • the protective layer is formed on the surface of the organic layer opposite to the surface on the substrate side.
  • the protective layer is preferably formed so as to be in direct contact with the organic layer, but other layers may be provided between the protective layers as long as the gist of the present invention is not deviated. Examples of the other layer include a fluorine-based undercoat layer and the like. Further, only one protective layer may be provided, or two or more protective layers may be provided.
  • the protective layer is preferably formed by using the composition for forming the protective layer. For details of the forming method, refer to the method of applying the protective layer forming composition in the above-mentioned laminate.
  • a photosensitive layer is formed on the surface of the protective layer opposite to the organic layer side (preferably on the surface).
  • the photosensitive layer is preferably formed by using the composition for forming the photosensitive layer.
  • the forming method refer to the method of applying the composition for forming a photosensitive layer in the above-mentioned laminate.
  • the photosensitive layer is exposed. Specifically, for example, at least a part of the photosensitive layer is irradiated (exposed) with active light rays. It is preferable that the exposure is performed so as to have a predetermined pattern. Further, the exposure may be performed through a photomask, or a predetermined pattern may be drawn directly.
  • the wavelength of the active ray at the time of exposure an active ray having a wavelength of 180 nm or more and 450 nm or less, more preferably 365 nm (i line), 248 nm (KrF line) or 193 nm (ArF line) can be used. can.
  • a low-pressure mercury lamp As the light source of the active light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a laser generator, a light emitting diode (LED) light source, or the like can be used.
  • a mercury lamp When a mercury lamp is used as a light source, active rays having wavelengths such as g-ray (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used, and i-ray is more preferable.
  • an active light having a wavelength of 343 nm and 355 nm is preferably used for a solid-state (YAG) laser, and 193 nm (ArF line), 248 nm (KrF line), and 351 nm (KrF line) for an excimer laser.
  • An active ray having a wavelength of (Xe line) is preferably used, and further, an active ray having a wavelength of 375 nm or 405 nm is preferably used in a semiconductor laser.
  • active rays having a wavelength of 355 nm or 405 nm are more preferable from the viewpoint of stability, cost and the like.
  • the laser can irradiate the photosensitive layer once or in a plurality of times.
  • the exposure amount is preferably 40 to 120 mJ, more preferably 60 to 100 mJ.
  • the energy density per pulse of the laser is preferably 0.1 mJ / cm 2 or more and 10,000 mJ / cm 2 or less.
  • 0.3 mJ / cm 2 or more is more preferable, and 0.5 mJ / cm 2 or more is further preferable.
  • the exposure amount is preferably set to 1,000 mJ / cm 2 or less, 100 mJ / cm 2 or less being more preferred.
  • the pulse width is preferably 0.1 nanosecond (hereinafter referred to as “ns”) or more and 30,000 ns or less.
  • ns 0.1 nanosecond
  • 0.5 ns or more is more preferable, and 1 ns or more is more preferable.
  • 1,000 ns or less is more preferable, and 50 ns or less is further preferable.
  • the frequency of the laser is preferably 1 Hz or more and 50,000 Hz or less, and more preferably 10 Hz or more and 1,000 Hz or less. Further, in order to shorten the exposure processing time, the laser frequency is more preferably 10 Hz or higher, further preferably 100 Hz or higher, and further preferably 10,000 Hz or lower in order to improve the matching accuracy during scan exposure. 000 Hz or less is more preferable.
  • the laser is preferable in that it is easier to focus than the mercury lamp, and the use of a photomask can be omitted in pattern formation in the exposure process.
  • the exposure apparatus is not particularly limited, but commercially available ones include Callisto (manufactured by V Technology Co., Ltd.), AEGIS (manufactured by V Technology Co., Ltd.), and DF2200G (Dainippon Screen Mfg. Co., Ltd.). It is possible to use (manufactured by). In addition, devices other than the above are also preferably used. Further, if necessary, the amount of irradiation light can be adjusted through a spectroscopic filter such as a long wavelength cut filter, a short wavelength cut filter, and a bandpass filter. Further, after the above exposure, a post-exposure heating step (PEB) may be performed if necessary.
  • PEB post-exposure heating step
  • Step (3) After exposing the photosensitive layer through a photomask, the photosensitive layer is developed using a developing solution. Negative type is preferable for development.
  • the details of the developer are as described in the above description of the photosensitive layer.
  • Examples of the developing method include a method of immersing the base material in a tank filled with a developing solution for a certain period of time (dip method), and a method of developing by raising the developing solution on the surface of the base material by surface tension and allowing it to stand still for a certain period of time.
  • the discharge pressure of the discharged developer (flow velocity per unit area of the discharged developer) is determined. It is preferably 2 mL / sec / mm 2 or less, more preferably 1.5 mL / sec / mm 2 or less, and further preferably 1 mL / sec / mm 2 or less. There is no particular lower limit on the discharge pressure, but 0.2 mL / sec / mm 2 or more is preferable in consideration of throughput.
  • the details of this mechanism are not clear, but probably, by setting the discharge pressure within the above range, the pressure applied to the photosensitive layer by the developer becomes small, and the resist pattern on the photosensitive layer is inadvertently scraped or broken. It is thought that this is because it is suppressed.
  • the discharge pressure of the developer (mL / sec / mm 2 ) is a value at the outlet of the developing nozzle in the developing apparatus. Examples of the method of adjusting the discharge pressure of the developing solution include a method of adjusting the discharge pressure with a pump and the like, a method of adjusting the pressure by supplying from a pressure tank, and the like.
  • a step of stopping the development while substituting with another organic solvent may be carried out.
  • Step of removing the protective layer and the organic layer of the non-masked portion After developing the photosensitive layer to prepare a mask pattern, at least the protective layer and the organic layer in the non-masked portion are removed by an etching process.
  • the non-masked portion refers to a region not masked by a mask pattern formed by developing the photosensitive layer (a region in which the photosensitive layer has been removed by development).
  • the etching process may be performed in a plurality of stages.
  • the protective layer and the organic layer may be removed by a single etching treatment, or after at least a part of the protective layer is removed by the etching treatment, the organic layer (and, if necessary, the protective layer) The balance) may be removed by etching.
  • the etching process may be a dry etching process or a wet etching process, and the etching may be divided into a plurality of times to perform the dry etching process and the wet etching process.
  • the removal of the protective layer may be by dry etching or wet etching.
  • Examples of the method for removing the protective layer and the organic layer include a method A in which the protective layer and the organic layer are removed by a single dry etching treatment, and at least a part of the protective layer is removed by a wet etching treatment. After that, a method such as method B for removing the organic layer (and, if necessary, the rest of the protective layer) by dry etching can be mentioned.
  • the dry etching treatment in the above method A, the wet etching treatment and the dry etching treatment in the above method B can be performed according to a known etching treatment method.
  • JP-A-2014-098889 can be referred to.
  • the protective layer and the organic layer of the non-masked portion can be removed by performing dry etching using the resist pattern as an etching mask (mask pattern).
  • Typical examples of dry etching are JP-A-59-126506, JP-A-59-046628, JP-A-58-009108, JP-A-58-002809, and JP-A57.
  • JP-A-59-126506, JP-A-59-046628, JP-A-58-009108, JP-A-58-002809, and JP-A57 There is a method described in Japanese Patent Application Laid-Open No. 148706 and Japanese Patent Application Laid-Open No. 61-041102.
  • the dry etching is preferably performed in the following form from the viewpoint of forming the cross section of the pattern of the organic layer to be formed closer to a rectangle and further reducing the damage to the organic layer.
  • a mixed gas of fluorine-based gas and oxygen gas (O 2 ) etching is performed to the region (depth) where the organic layer is not exposed, and after this first-stage etching, nitrogen gas ()
  • a second-stage etching that uses a mixed gas of N 2 ) and oxygen gas (O 2 ), preferably etching to the vicinity of the region (depth) where the organic layer is exposed, and over-etching that is performed after the organic layer is exposed.
  • a specific method of dry etching, as well as first-stage etching, second-stage etching, and over-etching will be described.
  • the etching conditions in dry etching are preferably performed while calculating the etching time by the following method.
  • A The etching rate (nm / min) in the first-stage etching and the etching rate (nm / min) in the second-stage etching are calculated, respectively.
  • B The time for etching the desired thickness in the first-stage etching and the time for etching the desired thickness in the second-stage etching are calculated, respectively.
  • C The first-stage etching is performed according to the etching time calculated in (B) above.
  • D The second stage etching is performed according to the etching time calculated in (B) above.
  • the etching time may be determined by endpoint detection, and the second-stage etching may be performed according to the determined etching time.
  • the overetching time is calculated with respect to the total time of the above (C) and (D), and the overetching is performed.
  • the mixed gas used in the first-stage etching preferably contains a fluorine-based gas and an oxygen gas (O 2 ) from the viewpoint of processing the organic material to be etched into a rectangular shape. Further, in the first-stage etching, the laminated body is etched to a region where the organic layer is not exposed. Therefore, it is considered that the organic layer is not damaged or the damage is slight at this stage.
  • the etching process using a mixed gas of nitrogen gas and oxygen gas from the viewpoint of avoiding damage to the organic layer.
  • the ratio of the etching amount in the second stage etching to the total etching amount is greater than 0% and 50% or less. Is preferable, and 10 to 20% is more preferable.
  • the etching amount refers to an amount calculated from the difference between the remaining film thickness of the film to be etched and the film thickness before etching.
  • the etching includes an over-etching process.
  • the over-etching treatment is preferably performed by setting the over-etching ratio.
  • the over-etching ratio can be set arbitrarily, but in terms of the etching resistance of the photoresist and the maintenance of the rectangularity of the pattern to be etched (organic layer), it is preferably 30% or less of the total etching treatment time in the etching process, and 5 to 5 to It is more preferably 25%, and particularly preferably 10 to 15%.
  • Examples of the method of removing the protective layer with the removing liquid include a method of spraying the removing liquid from a spray-type or shower-type injection nozzle onto the resist pattern to remove the protective layer.
  • examples of the injection nozzle include an injection nozzle in which the entire base material is included in the injection range, and a movable injection nozzle in which the movable range includes the entire base material.
  • Another embodiment is to mechanically remove the protective layer and then dissolve and remove the residue of the protective layer remaining on the organic layer.
  • the resist pattern is removed more effectively by injecting the removal liquid by moving from the center of the base material to the end of the base material twice or more during the process of removing the protective layer. be able to. It is also preferable to perform a step such as drying after removing the protective layer.
  • the drying temperature is preferably 80 to 120 ° C.
  • the kit of the present invention preferably contains the removing liquid of the present invention and the composition used for forming the protective layer.
  • the kit of the present invention is preferably a kit used for patterning an organic layer using a laminate.
  • the removing liquid contained in the kit of the present invention and the composition used for forming the protective layer composition for forming the protective layer
  • the kit of the present invention may further contain at least one of the above-mentioned composition for forming a photosensitive layer and the composition for forming an organic layer.
  • the semiconductor device of the present invention preferably contains a pattern in which the protective layer is removed from the above pattern by the removing liquid of the present invention.
  • the steps (3) to (5) described above are used as a method for forming a pattern formed by etching a laminate containing a base material, an organic layer, a protective layer, and a photosensitive layer in this order in the semiconductor device of the present invention. Examples include methods including. Further, a method including the steps described in (1) to (5) above may be used. Further, as a method for removing the protective layer from the above pattern by the removing liquid of the present invention, a method including the step described in (6) above can be mentioned.
  • the protective layer may be removed by the removing liquid of the present invention, and the protective layer and the removing liquid of the present invention may not remain in the semiconductor device.
  • the semiconductor device is a device containing a semiconductor and having two or more electrodes, and controlling the current flowing between the electrodes and the generated voltage by electricity, light, magnetism, chemical substances, or the like, or It is a device that generates light, electric field, magnetic field, etc. by the applied voltage and current. Examples include organic photoelectric conversion elements, organic field effect transistors, organic electroluminescent elements, gas sensors, organic rectifying elements, organic inverters, information recording elements, and the like.
  • the organic photoelectric conversion element can be used for both optical sensor applications and energy conversion applications (solar cells).
  • an organic field-effect transistor, an organic photoelectric conversion element, and an organic field-emitting element are preferable, an organic field-effect transistor and an organic photoelectric conversion element are more preferable, and an organic field-effect transistor is particularly preferable.
  • the removing liquid of the present invention is preferably used for manufacturing the above-mentioned semiconductor device.
  • composition for forming protective layer Each raw material was mixed so as to have the compounding ratio (part by mass) shown in the table below. After mixing, each of the protective layer forming compositions was stirred using a stirrer (hot magnet stirrer, C-MAG HS4, manufactured by IKA) under the following stirring conditions. After stirring is completed, a PVDF (polyvinylidene fluoride) membrane filter (Durapore, manufactured by Merck) with a pore size of 5 ⁇ m is installed in a stainless steel pressure filter holder (manufactured by Sartorius), and the pressure is applied at 2 MPa using this. While filtering each composition. [Stirring conditions] ⁇ Atmosphere: Atmosphere ⁇ Stirring time: 240 minutes ⁇ Stirring temperature: 50 ° C -Rotation speed of stirring member: 500 rpm (revolutions per minutes)
  • E-1 EMALEX 710 (manufactured by Nippon Emulsion Co., Ltd.)
  • E-2 Pionin D-1007 (manufactured by Takemoto Oil & Fat Co., Ltd.)
  • E-3 Pionin D-1105 (manufactured by Takemoto Oil & Fat Co., Ltd.)
  • E-4 Pionin D-1110 (manufactured by Takemoto Oil & Fats Co., Ltd.)
  • E-5 Pionin D-1420 (manufactured by Takemoto Oil & Fats Co., Ltd.)
  • E-6 Pionin D-2104-D (manufactured by Takemoto Oil & Fats Co., Ltd.)
  • E-7 Emargen 220 (manufactured by Kao Chemical Co., Ltd.)
  • E-8 Unilube MS-70K (manufactured by NOF)
  • E-9 Unigri MK-230 (manufactured
  • composition for forming photosensitive layer ⁇ Preparation of composition for forming photosensitive layer>
  • -Resin A-1 30.09 parts by mass-Photoacid generator (Compound X (structure below), R 11 represents a tolyl group, R 18 represents a methyl group.
  • Daito Chemix Co., Ltd. 0.26 parts by mass -Basic compound (Compound Y (structure below), manufactured by DSP Gokyo Food & Chemical Co., Ltd.): 0.08 parts by mass -Surfactant (manufactured by OMNOVA, PF-6320): 0.08 parts by mass-PGMEA (propylene glycol monomethyl ether acetate): 69.5 parts by mass
  • Resin A-1 was obtained by recovering the white powder produced by re-precipitating the reaction solution in heptane by filtration.
  • the weight average molecular weight (Mw) was 45,000.
  • an organic semiconductor coating liquid (composition for forming an organic semiconductor) having the following composition is spin-coated on a 5 cm square glass substrate and dried at 130 ° C. for 10 minutes to be organic. A semiconductor film was formed. The film thickness was 150 nm.
  • TOF-SIMS Time-of-Flight Secondary Ion Mass Spectrometry
  • ⁇ Composition of organic semiconductor coating liquid >> ⁇ P3HT (manufactured by Sigma-Aldrich Japan GK): 10% by mass ⁇ PCBM (manufactured by Sigma-Aldrich Japan GK): 10% by mass -Chloroform (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 80% by mass
  • the protective layer forming composition was spin-coated on the surface of the organic semiconductor film and dried at 100 ° C. for 1 minute to obtain the “film thickness ( ⁇ m)” in Table 1.
  • a protective layer having the thickness described in the column of is formed.
  • a 1: 1 line-and-space pattern having a line width of 2.0 ⁇ m and a line width of 20.0 ⁇ m was used as a photomask on the photosensitive layer in the produced laminate using an i-line exposure machine. It was exposed by i-line through a binary mask formed in 0.5 ⁇ m width increments. The exposure amount was set so that a line width of 2 ⁇ m could be obtained in a 1: 1 line-and-space pattern with a line width of 2 ⁇ m.
  • the exposed laminate was heated at 70 ° C. for 120 seconds, then developed with butyl acetate (nBA) as a developer for 60 seconds, and spin-dried to obtain a resist pattern. Further, it was developed with water for 20 seconds and spin-dried to obtain a pattern of a photosensitive layer and a protective layer.
  • nBA butyl acetate
  • the substrate was dry-etched under the following conditions to remove the organic layer in the non-mask pattern portion.
  • the temperature of the removing liquid was the temperature described in "Temperature (° C.)" of "Removing liquid” in the table.
  • Signal intensity ratio (%) [I / I 0 ] x 100 -Evaluation criteria- A: The signal intensity ratio (%) was 75% or more. B: The signal intensity ratio (%) was 50% or more and less than 75%. C: The signal intensity ratio (%) was 25% or more and less than 50%. D: The signal intensity ratio (%) was less than 25%.
  • Example 34 In Example 11, "the removal liquid is placed on the etched substrate prepared above, and after paddle cleaning for 60 seconds, the removal liquid is rotated at 2,000 rpm for 30 seconds to remove the removal liquid, and then the removal liquid is placed again for 60 seconds. After cleaning the paddle, the removal liquid was removed by rotating at 2,000 rpm for 30 seconds. "The removal liquid was placed on the etched substrate prepared above, and after paddle cleaning for 60 seconds, the removal liquid was removed at 2,000 rpm for 30 seconds. The residue was evaluated by the same method as in Example 11 except that the operation was changed to "rotate to remove the removing liquid” and the paddle washing using the removing liquid was changed from 2 times to 1 time.
  • the evaluation results are the evaluation in the part using the binary mask in which the 1: 1 line-and-space pattern with the line width of 2.0 ⁇ m is formed as the photomask, and the 1: 1 line-and-space pattern with the line width of 20.0 ⁇ m is formed. All of the evaluation results in the part using the obtained binary mask were C.
  • the removal liquid of the present invention is effective in removing the residue when the protective layer is removed.
  • the removal liquid used in Comparative Example 1 does not contain a surfactant for the removal liquid. It can be seen that when such a removing liquid is used, the suppression of the residue when the protective layer is removed is inferior.
  • a base material on which a gate electrode, a gate insulating film, a source electrode, and a drain electrode were formed was prepared by the same method as in Example 1 of International Publication No. 2018/061821.
  • An organic semiconductor layer, a protective layer, and a photosensitive layer were formed on the base material by the same method as shown in the residue evaluation in Examples 1 to 36 of the present invention, respectively.
  • the photosensitive layer is developed, the protective layer and the organic semiconductor layer are etched by the same method as the method shown in the residue evaluation, and the organic semiconductor layer is formed so as to be in contact with the source electrode and the drain electrode.
  • the organic field effect transistor operated normally.

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Abstract

L'invention concerne : un liquide d'élimination qui contient un tensioactif et qui est utilisé pour éliminer une couche protectrice contenue dans un motif formé par la gravure d'un corps en couches contenant, dans l'ordre donné, un substrat, une couche organique, la couche protectrice et une couche photosensible ; un kit qui contient le liquide d'élimination et une composition utilisée pour former la couche protectrice ; et un dispositif à semi-conducteur qui comprend le motif duquel la couche de protection a été éliminée à l'aide dudit liquide d'élimination.
PCT/JP2021/009000 2020-03-10 2021-03-08 Liquide d'élimination, kit, et dispositif à semi-conducteur WO2021182399A1 (fr)

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WO2024070946A1 (fr) * 2022-09-30 2024-04-04 富士フイルム株式会社 Composition, procédé de traitement d'un substrat, procédé de fabrication d'un dispositif à semi-conducteurs et composé

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WO2015064605A1 (fr) * 2013-10-31 2015-05-07 富士フイルム株式会社 Stratifié, kit de production de semi-conducteur organique et composition de réserve de production de semi-conducteur organique
WO2016017782A1 (fr) * 2014-08-01 2016-02-04 三菱化学株式会社 Procédé de fabrication d'un élément optique, élément optique obtenu au moyen dudit procédé, et dispositif d'affichage d'image pourvu dudit élément optique
JP2017063008A (ja) * 2015-09-26 2017-03-30 キヤノン株式会社 有機電子素子の製造方法

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JP2007119783A (ja) * 2005-10-27 2007-05-17 Mitsubishi Gas Chem Co Inc 洗浄液及び洗浄方法
JP2011222212A (ja) * 2010-04-07 2011-11-04 Konica Minolta Holdings Inc 有機電子デバイスの製造方法、有機電子デバイスおよびガスバリアフィルム前駆体
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WO2016017782A1 (fr) * 2014-08-01 2016-02-04 三菱化学株式会社 Procédé de fabrication d'un élément optique, élément optique obtenu au moyen dudit procédé, et dispositif d'affichage d'image pourvu dudit élément optique
JP2017063008A (ja) * 2015-09-26 2017-03-30 キヤノン株式会社 有機電子素子の製造方法

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WO2024070946A1 (fr) * 2022-09-30 2024-04-04 富士フイルム株式会社 Composition, procédé de traitement d'un substrat, procédé de fabrication d'un dispositif à semi-conducteurs et composé

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