Classifications

• • 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
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers
  • G03F7/322—Aqueous alkaline compositions
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
• • 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
  • G03F7/022—Quinonediazides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/16—Coating processes; Apparatus therefor
• • 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
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers
• • 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
  • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

• the present invention relates to a chemical solution and a pattern formation method.
• Patent Document 1 discloses a photosensitive composition containing magnetic particles that can be patterned.
• Patent Document 1 discloses a procedure for manufacturing a patterned substrate having a substrate and a pattern containing magnetic particles arranged on the substrate by subjecting a coating of a photosensitive composition containing magnetic particles formed on a substrate to an exposure process, an alkaline development process, and a rinsing process using water.
• the present inventors investigated a pattern formation method using a photosensitive composition containing magnetic particles and found that, since magnetic particles typically have a large specific gravity and are heavier than water, even after a rinsing process, magnetic particles that should be removed tend to remain on the surface of a patterned substrate and cause defects. In particular, with the recent trend toward finer patterns, stricter defect removal performance is required than ever before, and further improvements are needed to reduce the number of defects on patterned substrates.
• a chemical solution used in forming a pattern containing magnetic particles comprising: Water, A surfactant, A water-soluble organic solvent, The drug solution, wherein the surfactant includes a water-soluble polymer.
• the chemical solution according to [1] which is used as a rinsing solution after an alkaline development process when forming a pattern containing magnetic particles.
• the pattern forming method further comprises, when the composition is composition B, a step of performing a heat treatment on the substrate having the coating film rinsed with the chemical solution.
• [8] A step of applying a composition A containing magnetic particles, a resin, a polymerizable compound, and a solvent onto a substrate by an inkjet method or a screen method to form a patterned coating film; A step of subjecting the coating film to a curing treatment; and washing the substrate having the cured coating film thereon with the chemical solution according to any one of [1] to [6] above to form a pattern containing magnetic particles.
• a chemical solution that is excellent in removing defects on a patterned substrate that includes a substrate and a pattern containing magnetic particles. Furthermore, according to the present invention, a pattern forming method using the above-mentioned chemical solution can be provided.
• the present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.
• the notation of groups (atomic groups) that does not indicate whether they are substituted or unsubstituted includes both unsubstituted and substituted groups, unless it is contrary to the spirit of the present invention.
• alkyl group includes not only alkyl groups that do not have a substituent (unsubstituted alkyl groups), but also alkyl groups that have a substituent (substituted alkyl groups).
• organic group in the present specification refers to a group that contains at least one carbon atom.
• actinic rays or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light: extreme ultraviolet), X-rays, and electron beams (EB: electron beam), etc.
• light refers to actinic rays or radiation.
• exposure includes not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light, X-rays, EUV light, and the like, but also drawing with particle beams such as electron beams and ion beams.
• (meth)acrylate refers to acrylate and methacrylate
• (meth)acrylic refers to acrylic and methacrylic
• (meth)acryloyl refers to acryloyl and methacryloyl.
• solids of a composition refers to the components that form a magnetic material. Therefore, if the composition contains a solvent (organic solvent, water, etc.), it refers to all components excluding the solvent. Note that liquid components are also considered to be solids if they form a magnetic material.
• boiling point means the standard boiling point unless otherwise specified.
• weight average molecular weight (Mw) in this specification is a polystyrene equivalent value measured by the GPC (Gel Permeation Chromatography) method.
• each component may be used as a single substance corresponding to the component, or two or more substances may be used in combination.
• the content of that component refers to the total content of the substances used in combination, unless otherwise specified.
• the drug solution of the present invention is A chemical solution used in forming a pattern containing magnetic particles, Water, A surfactant, A water-soluble organic solvent,
• the surfactant includes a water-soluble polymer.
• the chemical solution of the present invention has the above-mentioned configuration, and is excellent in removing defects on a patterned substrate that includes a substrate and a pattern containing magnetic particles.
• a patterned substrate including a substrate and a pattern including magnetic particles
• the magnetic particles remaining on the substrate often have components such as dispersants that improve the dispersibility of the particles desorbed. Therefore, even if the substrate is washed with water, the magnetic particles are poorly dispersible in water and are difficult to remove from the substrate.
• the chemical solution of the present invention when used in the manufacture of a substrate including a substrate and a pattern including magnetic particles, the magnetic particles on the substrate are easily redispersed in the solvent by being wrapped in a water-soluble polymer, and as a result, the number of defects resulting from the magnetic particles remaining on the substrate can be reduced.
• the chemical solution of the present invention is excellent in removing defects on a substrate including a substrate and a pattern including magnetic particles.
• the chemical solution of the present invention when applied to a pattern formation method for manufacturing a patterned substrate by a pattern formation method including an exposure process, a development process, and a rinsing process, the chemical solution of the present invention is also excellent in removing magnetic particle residues adhering to the sidewalls and drain of the developing cup. In other words, it is possible to wash away magnetic particle residues adhering to the sidewalls and drain of the developing cup, and furthermore, it is possible to suppress the accumulation of magnetic particles at the bottom of the developing cup and clogging of piping.
• the superior ability to remove defects on a patterned substrate which includes a substrate and a pattern containing magnetic particles, is also referred to as "the effect of the present invention being superior.”
• the chemical solution includes water.
• water water that has been subjected to a purification treatment, such as distilled water, ion-exchanged water, and ultrapure water, is preferable, and ultrapure water used in semiconductor manufacturing is more preferable.
• the lower limit of the water content in the chemical solution is preferably 60.0% by mass or more, more preferably 65.0% by mass or more, and even more preferably 70.0% by mass or more, and the upper limit is preferably 95.0% by mass or less, more preferably 90.0% by mass or less, even more preferably 85.0% by mass or less, and particularly preferably 80.0% by mass or less.
• the chemical solution contains a surfactant.
• a surfactant is a compound that has a hydrophilic group and a hydrophobic group (lipophilic group) in the molecule.
• the surfactant contained in the chemical solution may be, for example, any one of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant.
• the lower limit of the content of the surfactant in the chemical solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.10% by mass or more, and the upper limit is preferably 3.0% by mass or less, more preferably 1.5% by mass or less, even more preferably 1.0% by mass or less, and particularly preferably 0.5% by mass or less.
• the surfactant may be used alone or in combination with two or more kinds. When two or more kinds are used, the total content is preferably within the above-mentioned preferred content range.
• the chemical solution contains a water-soluble polymer as a surfactant.
• water-soluble means having a solubility in water (20° C.) of 0.5 g/1 L or more.
• the water-soluble polymer is preferably a nonionic surfactant. Of these, the water-soluble polymer is more preferably a compound having a polyoxyalkylene structure.
• the polyoxyalkylene structure is a structure represented by -(A-O)n- (A represents an alkylene group, and n represents the average number of additions, for example, a number from 2 to 100). Examples of the oxyalkylene group represented by A-O include an ethylene oxide group and a propylene oxide group.
• the polyoxyalkylene structure may contain multiple types of oxyalkylene groups. The polyoxyalkylene structure may be contained in the main chain or in a side chain.
• compounds having a polyoxyalkylene structure include polypropylene glycol ethylene oxide adducts; dimethylsiloxane-ethylene oxide block copolymers; dimethylsiloxane-(propylene oxide-ethylene oxide) block copolymers; polyethylene glycol-type higher alcohol ethylene oxide adducts; fatty acid ethylene oxide adducts; higher alkylamine ethylene oxide adducts; fatty acid amide ethylene oxide adducts, etc.
• water-soluble polymers other than compounds having a polyoxyalkylene structure such as lysozyme, a glycolytic enzyme, can also be used.
• the lower limit of the weight average molecular weight (Mw) of the water-soluble polymer is preferably 50 or more.
• the upper limit is preferably 100,000 or less, more preferably 30,000 or less, and even more preferably 10,000 or less.
• the lower limit of the number average molecular weight (Mn) of the water-soluble polymer is preferably 10 or more.
• the upper limit is preferably 1,000 or less, more preferably 500 or less, and even more preferably 200 or less.
• Water-soluble polymer products include “Poloxamer 407” (manufactured by Sigma-Aldrich; a polymer with a poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) structure); “Marialim SC0505K,” “Dispanol WI-133,” and “Esream AD3172M” (all manufactured by NOF Corp.; polymers with polyoxyalkylene groups in the side chains); and “Olfine E1010” (manufactured by Nissin Chemical; polyoxyethylene (10) acetylenic glycol ether).
• the lower limit of the content of the water-soluble polymer in the drug solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.10% by mass or more.
• the upper limit is preferably 3.0% by mass or less, more preferably 1.5% by mass or less, even more preferably 1.0% by mass or less, and particularly preferably 0.5% by mass or less.
• the water-soluble polymer may be used alone or in combination of two or more kinds. When two or more kinds are used, it is preferable that the total content is within the range of the preferred content described above.
• surfactants other than the water-soluble polymer compounds known as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be used, with nonionic surfactants being preferred.
• surfactants other than water-soluble polymers include, for example, ethylene oxide adducts of alkylphenols; polyethylene glycol adducts of aromatic compounds; ethylene oxide adducts of polyhydric alcohol fatty acid esters; ethylene oxide adducts of fats and oils; polyhydric alcohol-type fatty acid esters of glycerol; fatty acid esters of pentaerythritol; fatty acid esters of sorbitol and sorbitan; fatty acid esters of sucrose; alkyl ethers of polyhydric alcohols; and fatty acid amides of alkanolamines.
• surfactants other than water-soluble polymers examples include “Surfynol 104E” and “Surfynol 440” (manufactured by Nissin Chemical Industry, polyether of acetylene-based dialcohol).
• Water-soluble organic solvent The chemical solution contains a water-soluble organic solvent.
• water-soluble means having a solubility in water (20° C.) of 0.5 g/1 L or more.
• water-soluble organic solvent examples include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, 2-methoxypropanol, ethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), dipropylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate (PGMEA).
• water-soluble organic solvent among others, a monohydric alcohol (alcohol having only one hydroxy group) is preferable, an aliphatic alcohol is more preferable, an aliphatic alcohol having 5 or less carbon atoms is even more preferable, ethanol or methanol is particularly preferable, and ethanol is most preferable.
• a monohydric alcohol alcohol having only one hydroxy group
• an aliphatic alcohol is more preferable
• an aliphatic alcohol having 5 or less carbon atoms is even more preferable
• ethanol or methanol is particularly preferable
• ethanol is most preferable.
• the lower limit of the content of the water-soluble organic solvent in the chemical solution is preferably 10.0% by mass or more, more preferably 15.0% by mass or more, and even more preferably 18.0% by mass or more, and the upper limit is preferably 40.0% by mass or less, more preferably 35.0% by mass or less, and even more preferably 30.0% by mass or less.
• the water-soluble organic solvent may be used alone or in combination of two or more. When two or more types are used, the total content is preferably within the above-mentioned preferred content range.
• the chemical solution preferably contains a polyhydric alcohol.
• the polyhydric alcohol is not particularly limited as long as it is a dihydric or higher alcohol, but alkylene glycol, polyoxyalkylene glycol, or glycerin is preferred.
• the number of carbon atoms in the alkyl group portion of the alkylene glycol is preferably 1 to 4, and more preferably 2 or 3.
• the alkyl group portion is preferably linear or branched.
• the number of carbon atoms in the oxyalkylene group is preferably 1 to 4, and more preferably 2 or 3.
• the oxyalkylene group is preferably linear or branched.
• the number of repetitions of the oxyalkylene group is preferably 2 to 4.
• Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, and glycerin.
• the lower limit of the content of the polyhydric alcohol in the chemical solution is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, and the upper limit is preferably 15.0% by mass or less, more preferably 10.0% by mass or less, and even more preferably 8.0% by mass or less.
• the polyhydric alcohol may be used alone or in combination of two or more. When two or more types are used, the total content is preferably within the above-mentioned preferred content range.
• the chemical solution preferably contains a pH adjuster selected from the group consisting of organic amines and their salts, and organic acids and their salts.
• a pH adjuster selected from the group consisting of organic amines and their salts, and organic acids and their salts.
• Organic amines and their salts are compounds or salts thereof that have at least one amino group selected from the group consisting of a primary amino group (-NH 2 ), a secondary amino group (>NH), a tertiary amino group (>N-), and a quaternary ammonium group (>N + ⁇ ) in the molecule.
• the organic amine may be a low molecular weight compound or a high molecular weight compound, but a low molecular weight compound is preferred in terms of obtaining better effects of the present invention.
• the number of amino groups contained in the organic amine is, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
• the organic amine may be linear, branched, or cyclic.
• Examples of organic amines and salts thereof include alkanolamines, alicyclic amines, aliphatic amines, aromatic amines, and quaternary ammonium salts.
• Alkanolamines are organic amines that further have at least one hydroxylalkyl group in the molecule.
• the alkanolamines may have any of primary, secondary and tertiary amino groups, but preferably have a primary amino group.
• the number of amino groups that the alkanolamine has is, for example, 1 to 5, and preferably 1 to 3.
• the number of hydroxy groups that the alkanolamine has is, for example, 1 to 5, and more preferably 1 to 3. Among them, it is more preferable that the alkanolamine has only primary amino groups as amino groups.
• Specific examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, and isopropanolamine.
• alicyclic amines examples include morpholine and N-hydroxyethylmorpholine.
• Examples of the aliphatic amine include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, ethylenediamine, trimethylenediamine, and polyethyleneimine.
• Commercially available polyethyleneimine products include "Epomin P1000" (manufactured by Nippon Kayaku Co., Ltd.).
• Aromatic amines include pyridine, aniline, N,N-dimethylaniline, N,N-diethylaniline, and N,N-diethanolaniline.
• quaternary ammonium salts include quaternary ammonium hydroxides, quaternary ammonium fluorides, quaternary ammonium bromides, quaternary ammonium iodides, quaternary ammonium acetates, and quaternary ammonium carbonates, and among these, quaternary ammonium hydroxides are preferred.
• the quaternary ammonium salt is preferably a tetraalkylammonium salt, and the number of carbon atoms in each of the four alkyl groups is preferably 1 to 6, and more preferably 1 to 3.
• a specific example of the quaternary ammonium salt is tetramethylammonium hydroxide.
• the organic acid refers to an organic compound that, when dissolved in water to form an aqueous solution, exhibits acidity in the resulting aqueous solution.
• the acid dissociation constant (pKa) of the organic acid is preferably 10.0 or less, more preferably 5.0 or less.
• the lower limit of the acid dissociation constant of the organic acid is -2.0 or more, and preferably 0.0 or more.
• a compound having an amino group is considered to be an organic acid.
• the organic acid includes an organic compound having one or more acid groups in the molecule, and examples of the acid group include a carboxylic acid group, a phosphonic acid group, a phosphoric acid group, a sulfonic acid group, and a sulfamic acid group.
• the acid group of the organic acid may have a salt structure.
• the salt of the organic acid is not particularly limited, but may be an alkali metal salt such as potassium salt or sodium salt; an alkaline earth metal salt such as calcium salt or magnesium salt; an amine salt; or an ammonium salt.
• the salt of the organic acid may have a betaine structure (inner salt).
• organic acids and their salts include organic carboxylic acids and their salts, organic sulfonic acids and their salts, organic phosphonic acids and their salts, organic phosphoric acids and their salts, and sulfamic acids and their salts, among which organic carboxylic acids and their salts are preferred in that they provide a better effect for the present invention.
• the organic acid is also preferably one having a hydroxy group in the molecule.
• the organic acid has a hydroxy group in the molecule, the number of the hydroxy groups is, for example, 1 to 6.
• the organic acid is preferably an aliphatic organic acid.
• the organic carboxylic acid is preferably an aliphatic carboxylic acid.
• the number of carboxy groups in the organic carboxylic acid may be 1 or more. That is, the organic carboxylic acid may be an aliphatic monocarboxylic acid or an aliphatic polycarboxylic acid. In the aliphatic polycarboxylic acid, the upper limit of the number of carboxy groups is 5 or less, more preferably 4 or less, and more preferably 3 or less.
• the organic carboxylic acid may have a substituent other than the carboxy group (for example, a hydroxy group).
• the aliphatic monocarboxylic acid is preferably a compound represented by the following formula (X1).
• R X1 -COOH (X1) R X1 represents an alkyl group having 1 to 6 carbon atoms.
• the alkyl group represented by R X1 may be linear, branched, or cyclic.
• the methylene group constituting the alkyl group represented by R X1 may be substituted with -O-.
• Examples of the alkyl group represented by R X1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a cyclohexyl group.
• the compound represented by formula (X1) includes acetic acid and the like.
• the aliphatic polycarboxylic acid is preferably a compound represented by the following formula (X2). HOOC-R X2 -COOH (X2)
• R X2 represents a single bond or an alkylene group having 1 to 6 carbon atoms.
• the alkylene group represented by R X2 may be linear, branched, or cyclic.
• a methylene group constituting the alkylene group represented by R X2 may be substituted with -O-.
• a hydrogen atom in the alkyl group represented by R X2 may be substituted with a carboxy group.
• Examples of the alkylene group represented by R X2 include a methylene group, an ethylene group, a propylene group, a butylene group, and a cyclohexylene group.
• Examples of the compound represented by formula (X2) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and cyclohexanedicarboxylic acid.
• the aliphatic hydroxymonocarboxylic acid is preferably a compound represented by the following formula (X3).
• R X3 -COOH (X3) R X3 represents an alkyl group having 1 to 6 carbon atoms and having a hydroxy group.
• the alkyl group having a hydroxy group represented by R X3 may be linear, branched, or cyclic.
• a methylene group constituting the alkyl group having a hydroxy group represented by R X3 may be substituted with -O-.
• Examples of the alkyl group having a hydroxy group represented by R X3 include a group in which one or more hydrogen atoms of the alkyl group represented by R X1 are substituted with a hydroxy group.
• Examples of the compound represented by formula (X3) include glycolic acid, lactic acid, glyceric acid, hydroxybutyric acid, gluconic acid, and glucuronic acid.
• the aliphatic hydroxypolycarboxylic acid is preferably a compound represented by the following formula (X4).
• HOOC-R X4 -COOH (X4)
• R X4 represents an alkylene group having 1 to 6 carbon atoms and a hydroxy group.
• the alkylene group having a hydroxy group represented by R X4 may be linear, branched, or cyclic.
• a methylene group constituting the alkylene group having a hydroxy group represented by R X4 may be substituted with -O-.
• a hydrogen atom in the alkyl group having a hydroxy group represented by R X4 may be substituted with a carboxy group.
• Examples of the alkylene group having a hydroxy group represented by R 4 include groups in which one or more hydrogen atoms of the alkylene group represented by R 4 X2 have been substituted with a hydroxy group.
• Examples of the compound represented by formula (X4) include tartaric acid, malic acid, tartaric acid, and citric acid.
• examples of organic carboxylic acids other than the compounds represented by the above formulas (X1) to (X4) include higher fatty acids having 12 or more carbon atoms.
• examples of higher fatty acids having 12 or more carbon atoms include higher fatty acids having 12 to 18 carbon atoms, and among these, lauric acid is preferred.
• the organic carboxylic acid other than the above-mentioned organic carboxylic acids may be an amino acid, which is an organic compound having an amino group and a carboxy group in the molecule.
• amino acids include ⁇ -amino acids having an amino group at the carbon atom ( ⁇ carbon) to which a carboxy group is bonded, ⁇ -amino acids having an amino group at the carbon atom ( ⁇ carbon) bonded to the ⁇ carbon, and ⁇ -amino acids having an amino group at the carbon atom ( ⁇ carbon) bonded to the ⁇ carbon.
• amino acids include arginine, asparagine, glutamine, histidine, lysine, hydroxylysine, and tryptophan.
• the organic carboxylic acid is preferably one or more selected from the group consisting of acetic acid, tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, and gluconic acid, and more preferably citric acid.
• organic sulfonic acids and their salts examples include aliphatic sulfonic acids such as alkylsulfonic acids and ⁇ -olefinsulfonic acids; aromatic sulfonic acids; and alkyl ether sulfuric acids.
• the alkylsulfonic acid may, for example, be an alkylsulfonic acid having 12 to 20 carbon atoms.
• the alkylsulfonic acid may, for example, be octadecyl sulfate.
• the ⁇ -olefin sulfonic acid may, for example, be an ⁇ -olefin sulfonic acid having 14 to 16 carbon atoms.
• aromatic sulfonic acids include substituted or unsubstituted benzenesulfonic acid.
• Substituents include halogen atoms, alkyl groups, alkoxy groups, alkylcarbonyloxy groups, thiol groups, and hydroxyl groups.
• Specific examples of aromatic sulfonic acids include toluenesulfonic acid and benzenesulfonic acid.
• Examples of the alkyl ether sulfate include polyoxyethylene alkyl ether sulfate.
• the organic sulfonic acid is preferably in the form of a salt, and more preferably in the form of an alkali metal salt.
• the organic sulfamic acid includes alkylsulfamic acids, for example, alkylsulfamic acids having 12 to 20 carbon atoms.
• the organic sulfamic acid is preferably in the form of a salt, and more preferably in the form of an alkali metal salt.
• the organic phosphonic acid may be an aromatic phosphonic acid.
• the aromatic phosphonic acid may be, for example, a substituted or unsubstituted phenylphosphonic acid.
• the substituent may be a halogen atom, an alkyl group, an alkoxy group, an alkylcarbonyloxy group, a thiol group, or a hydroxyl group.
• the specific example of the aromatic phosphonic acid may be phenylphosphonic acid.
• the organic phosphoric acid includes alkyl phosphoric acids, for example, alkyl phosphoric acids having 12 to 20 carbon atoms.
• the lower limit of the content of the pH adjuster in the chemical solution is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.05% by mass or more, and the upper limit is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.0% by mass or less.
• the pH adjuster may be used alone or in combination with two or more kinds. When two or more kinds are used, the total content is preferably within the above-mentioned preferred content range.
• Examples of other components that may be contained in the chemical solution include anticorrosive agents, bactericides, antibacterial agents, disinfectants, and antifoaming agents.
• the chemical solution may contain a surfactant other than the water-soluble polymer.
• the pH of the chemical solution may be either acidic or basic.
• the pH is preferably 1 to 6, and more preferably 1 to 4.
• the chemical solution is basic, the pH is preferably 8 to 14, and more preferably 10 to 14.
• the pH of the chemical solution is within the above range, the surface charge of the magnetic particles taken into the chemical solution during washing in pattern formation becomes large, and the magnetic particles are more likely to be dispersed in the chemical solution. As a result, the effects of the present invention are more likely to be excellent.
• the pH of the chemical solution is obtained by measurement at 25° C. using a pH meter (F-51 (product name), manufactured by Horiba, Ltd.). Examples of methods for adjusting the pH include a method of adjusting the type and content of each component that may be contained in the chemical solution, and a method of adding the above-mentioned pH adjuster.
• An example of a suitable embodiment of the chemical solution includes a composition containing water; a surfactant including a water-soluble polymer; a water-soluble organic solvent; a pH adjuster selected from the group consisting of organic amines and their salts, and organic acids and their salts; and a polyhydric alcohol.
• An example of a suitable embodiment of the chemical solution is one in which the combined content of water and the water-soluble organic solvent is 90.0% by mass or more (preferably 95.0% by mass or more) based on the total mass of the composition.
• the method for producing the drug solution is not particularly limited, and the drug solution can be prepared by mixing the above-mentioned components.
• the order and/or timing of mixing the above components is not particularly limited, and for example, the water-soluble polymer and the water-soluble organic solvent may be added in sequence to a container containing water, and then the mixture may be stirred and mixed. After mixing, a pH adjuster may be added to adjust the pH of the mixture. When water and each component are added to a container, they may be added all at once, or may be added in multiple portions in separate portions.
• the stirring device and stirring method used to prepare the chemical solution may be a device known as a stirrer or disperser.
• stirrers include industrial mixers, portable stirrers, mechanical stirrers, and magnetic stirrers.
• dispersers include industrial dispersers, homogenizers, ultrasonic dispersers, and bead mills.
• purification processes include known methods such as distillation, ion exchange, and filtration.
• the mixing of the components in the preparation process of the chemical solution, the purification process, and the storage of the produced chemical solution are preferably carried out at 40°C or less, and more preferably at 30°C or less.
• the lower limit is preferably 5°C or more, and more preferably 10°C or more.
• the chemical liquid can be used as a cleaning liquid for removing magnetic particles remaining on the surface of a patterned substrate when a pattern containing magnetic particles is formed.
• the method for forming a pattern containing magnetic particles is not particularly limited, and examples thereof include various methods such as a lithography method using a photosensitive composition containing magnetic particles, as well as an inkjet method and a screen method.
• the chemical solution is preferably used as a rinse liquid in a rinse process carried out after an exposure process and a development process, and more preferably used as a rinse liquid in a rinse process carried out after an exposure process and an alkaline development process.
• the method for forming a pattern containing magnetic particles is an inkjet method or a screen method, it is preferable to use the composition as a cleaning liquid when cleaning a pattern-shaped coating film containing magnetic particles formed on a substrate after a curing treatment.
• the pattern formation method of the first embodiment includes steps X1, X2, X3, and X4, and further, when the composition is composition B, it is preferable that step X4 further includes a step of performing a heat treatment on the substrate having the coating film rinsed with the chemical solution. That is, the pattern formation method of the first embodiment includes steps X1, X2, X3, and X4 when the composition is composition A, and preferably includes steps X1, X2, X3, and X5 when the composition is composition B.
• Step X1 A step of applying any one of composition A containing magnetic particles, a resin, a polymerizable compound, and a solvent, and composition B containing magnetic particles, a resin, a compound that is alkali-soluble upon light irradiation, a crosslinking agent, and a solvent onto a substrate to form a coating film;
• Step X2 A step of patternwise exposing the coating film;
• Step X3 A step of alkaline-developing the patternwise exposed coating film;
• Step X4 A step of rinsing the substrate having the alkaline-developed coating film with a chemical solution to form a pattern containing magnetic particles;
• Step X5 A step of rinsing the substrate having the alkaline-developed coating film with a chemical solution, and further performing a heat treatment on the substrate having the coating film that has been rinsed with the chemical solution to form a pattern containing magnetic particles.
• Steps X1 to X5 are explained below.
• Step X1 is a step of applying a composition containing components such as magnetic particles onto a substrate to form a coating film.
• the composition may be either a negative-type photosensitive composition or a positive-type photosensitive composition.
• the composition will be described later.
• the substrate is not particularly limited, and may be a substrate used in the manufacture of integrated circuit elements, such as a silicon substrate, a silicon dioxide-coated substrate, or a polyimide substrate, with a silicon wafer being preferred.
• a member such as an antenna may be disposed on the substrate.
• the composition can be applied to a substrate by various coating methods, such as slit coating, inkjet coating, rotary coating using a spinner or coater, casting coating, roll coating, and screen printing.
• the lower limit of the coating thickness is, for example, preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 15 ⁇ m or more.
• the upper limit is preferably 10,000 ⁇ m or less, more preferably 1,000 ⁇ m or less, even more preferably 800 ⁇ m or less, and particularly preferably 300 ⁇ m or less.
• the coating film disposed on the substrate may be subjected to a heat treatment (pre-baking).
• the heating temperature is, for example, preferably 50 to 140°C, and more preferably 80 to 120°C.
• the heating time is, for example, preferably 30 to 1800 seconds, more preferably 60 to 1000 seconds, and even more preferably 60 to 800 seconds.
• Step X2 is a step of subjecting the coating film obtained in step X1 to pattern exposure.
• the method of exposure is not particularly limited, but it is preferable to irradiate the coating film with light through a photomask having patterned openings.
• the exposure is preferably carried out by irradiation with radiation. Examples of radiation that can be used for the exposure include ultraviolet rays such as g-rays, h-rays, and i-rays, and a high-pressure mercury lamp is preferred as the light source.
• the irradiation intensity is preferably 5 to 1500 mJ/ cm2 , and more preferably 10 to 1000 mJ/ cm2 .
• Step X3 is a step of alkaline developing the pattern-exposed coating film.
• a negative pattern can be formed by step X3.
• a positive pattern can be formed by step X3.
• Examples of the developing method include a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (dip method), a method of piling up the developing solution on the substrate surface by surface tension and leaving it to stand for a certain period of time to develop (paddle method), a method of spraying the developing solution on the substrate surface (spray method), and a method of continuously discharging the developing solution while scanning a developing solution dispensing nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method).
• dip method dip method
• spray method a method of spraying the developing solution on the substrate surface
• dynamic dispense method a method of continuously discharging the developing solution while scanning a developing solution dispensing nozzle at a constant speed onto a substrate rotating at a constant speed
• the development time is not particularly limited as long as it is a time sufficient to dissolve the coating film in the unexposed areas, and is preferably from 10 to 300 seconds, more preferably from 20 to 120 seconds, and even more preferably from 20 to 90 seconds.
• the temperature of the developer is preferably from 0 to 50°C, more preferably from 15 to 35°C, and even more preferably from 20 to 30°C.
• the type of developer used in the development process is not particularly limited, but an alkaline developer is preferred.
• the alkaline developer is preferably an alkaline aqueous solution prepared by dissolving an alkaline compound in water to a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass).
• alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene (among these, organic alkalis are preferred).
• Step X4 is a step of rinsing the substrate with the coating film obtained through step X3 with a chemical solution to form a pattern containing magnetic particles.
• a chemical solution is used as a rinsing liquid.
• the chemical solution is as described above. After the rinsing process using the chemical solution is performed, it is also preferable to further perform a rinsing process using pure water.
• the rinsing method is not particularly limited, and examples thereof include a method of continuously discharging a rinsing liquid onto a substrate rotating at a constant speed (spin coating method), a method of immersing a substrate in a tank filled with the rinsing liquid for a certain period of time (dip method), and a method of spraying the rinsing liquid onto the substrate surface (spray method).
• the rinsing time is not particularly limited, but is preferably from 10 to 300 seconds, more preferably from 20 to 120 seconds, and even more preferably from 20 to 90 seconds.
• the temperature of the rinse solution is preferably from 0 to 50°C, more preferably from 15 to 35°C, and even more preferably from 20 to 30°C.
• Step X5 is a step of rinsing the substrate with the coating film obtained through step X3 with a chemical solution, and further performing a heat treatment on the substrate with the coating film rinsed with the chemical solution to form a pattern containing magnetic particles.
• a chemical solution is used as a rinsing solution.
• the chemical solution is as described above. It is also preferable to carry out a rinse treatment with pure water after carrying out the rinse treatment using the chemical solution and before carrying out the heat treatment.
• the rinsing method is not particularly limited, and examples thereof include a method of continuously discharging a rinsing liquid onto a substrate rotating at a constant speed (spin coating method), a method of immersing a substrate in a tank filled with the rinsing liquid for a certain period of time (dip method), and a method of spraying the rinsing liquid onto the substrate surface (spray method).
• the rinsing time is not particularly limited, but is preferably from 10 to 300 seconds, more preferably from 20 to 120 seconds, and even more preferably from 20 to 90 seconds.
• the temperature of the rinse solution is preferably from 0 to 50°C, more preferably from 15 to 35°C, and even more preferably from 20 to 30°C.
• the substrate having the coating film rinsed with the chemical solution is subjected to a heat treatment.
• the heating temperature is preferably from 80 to 150°C, more preferably from 80 to 140°C, and even more preferably from 80 to 130°C.
• the heating time is preferably from 10 to 1,000 seconds, more preferably from 10 to 180 seconds, and even more preferably from 30 to 120 seconds. Heating can be carried out by a means provided in a normal exposure machine and/or developing machine, and may be carried out using a hot plate or the like.
• the step X4 may include a step of performing a heating step (step X6) on the substrate having the coating film rinsed with the chemical solution after the rinsing treatment.
• step X6 a heating step
• the upper limit of the heating temperature is preferably 240° C. or lower, and more preferably 220° C. or lower.
• the lower limit is preferably 50° C. or higher, and more preferably 100° C. or higher.
• the heating can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (a hot air circulation type dryer), or a high-frequency heater.
• Step X7 After carrying out step X2 and before carrying out step X3, it is also preferable to carry out a heat treatment (step X7) on the coating film that has been subjected to the exposure treatment.
• the heating temperature is preferably from 80 to 150°C, more preferably from 80 to 140°C, and even more preferably from 80 to 130°C.
• the heating time is preferably from 10 to 1,000 seconds, more preferably from 10 to 180 seconds, and even more preferably from 30 to 120 seconds. Heating can be carried out by a means provided in a normal exposure machine and/or developing machine, and may be carried out using a hot plate or the like.
• the pattern formation method of the second embodiment includes the following steps Y1 to Y3.
• Step Y1 A step of applying a composition A containing magnetic particles, a resin, a polymerizable compound, and a solvent onto a substrate by an inkjet method or a screen method to form a patterned coating film.
• Step Y2 A step of subjecting the coating film to a curing treatment.
• Step Y3 A step of washing the substrate having the cured coating film (patterned cured film) with a chemical solution to form a pattern containing magnetic particles.
• Step Y1 is a step of applying a composition containing components such as magnetic particles onto a substrate to form a coating film.
• the composition will be described in detail later.
• the composition and substrate used may be the same as those used in step X1 of the pattern formation method of the first embodiment described above.
• a patterned coating of a composition containing components such as magnetic particles is formed on a substrate by an ink-jet method or a screen method.
• the lower limit of the thickness of the coating film is, for example, preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and even more preferably 15 ⁇ m or more.
• the upper limit is preferably 10,000 ⁇ m or less, more preferably 1,000 ⁇ m or less, even more preferably 800 ⁇ m or less, and particularly preferably 300 ⁇ m or less.
• Step Y2 is a step of performing a curing treatment on the pattern-shaped coating film obtained in step Y1.
• the curing treatment includes exposure treatment and heat treatment, and exposure treatment is preferred.
• the coating film disposed on the substrate may be subjected to a heat treatment (pre-bake).
• the heating temperature is, for example, preferably 50 to 140°C, and more preferably 80 to 120°C.
• the heating time is, for example, preferably from 30 to 1800 seconds, more preferably from 60 to 1000 seconds, and even more preferably from 60 to 800 seconds.
• the method of the exposure treatment is the same as the method of the exposure treatment explained in step X2 of the pattern formation method of the first embodiment described above.
• Step Y3 is a step of cleaning the substrate having the patterned cured film obtained in step Y2 with a chemical solution to form a pattern containing magnetic particles.
• a chemical solution is used as the cleaning solution.
• the chemical solution is as described above. It is also preferable to carry out a cleaning process using pure water after carrying out the cleaning process using the chemical solution.
• the cleaning method is not particularly limited, and examples thereof include a method in which a cleaning liquid is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with a cleaning liquid for a certain period of time (dip method), and a method in which a cleaning liquid is sprayed onto the substrate surface (spray method).
• the cleaning time is not particularly limited, but is preferably from 10 to 300 seconds, more preferably from 20 to 120 seconds, and even more preferably from 20 to 90 seconds.
• the temperature of the cleaning solution is preferably from 0 to 50°C, more preferably from 15 to 35°C, and even more preferably from 20 to 30°C.
• step Y4 When step Y2 is an exposure treatment, it is also preferable to carry out a heat treatment (step Y4) on the coating film that has been subjected to the exposure treatment after carrying out step Y2 and before carrying out step Y3.
• the heating temperature is preferably from 80 to 150°C, more preferably from 80 to 140°C, and even more preferably from 80 to 130°C.
• the heating time is preferably from 10 to 1,000 seconds, more preferably from 10 to 180 seconds, and even more preferably from 30 to 120 seconds. Heating can be carried out by a means provided in a normal exposure machine and/or developing machine, and may be carried out using a hot plate or the like.
• the process Y3 may include a process of performing a heating process (process Y5) on the substrate having the coating film rinsed with the chemical solution after the rinsing process. By performing the process Y5, the cleaning solution remaining between the patterns and inside the patterns can be removed.
• the upper limit of the heating temperature is preferably 240° C. or lower, and more preferably 220° C. or lower.
• the lower limit is preferably 50° C. or higher, and more preferably 100° C. or higher.
• the heating can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater.
• compositions composition A and composition B
• composition A and composition B compositions that can be used in the above-mentioned pattern forming method will be described in detail below.
• the magnetic particles contain metal atoms.
• the metal atoms also include metalloid atoms such as boron, silicon, germanium, arsenic, antimony, and tellurium.
• the metal atoms may be contained in the magnetic particles as an alloy containing the metal element (preferably a magnetic alloy), a metal oxide (preferably a magnetic oxide), a metal nitride (preferably a magnetic oxide), or a metal carbide (preferably a magnetic carbide).
• the content of the metal atoms relative to the total mass of the magnetic particles is preferably from 50 to 100% by mass, more preferably from 75 to 100% by mass, and even more preferably from 95 to 100% by mass.
• the metal atom is not particularly limited, but preferably contains at least one metal atom selected from the group consisting of Fe, Ni, and Co.
• the content of at least one metal atom selected from the group consisting of Fe, Ni and Co (when multiple types are included, the total content) is preferably 50 mass% or more, more preferably 60 mass% or more, and even more preferably 70 mass% or more, based on the total mass of metal atoms in the magnetic particle.
• the upper limit of the content is not particularly limited, and is, for example, 100 mass% or less, preferably 98 mass% or less, and more preferably 95 mass% or less.
• the magnetic particles may contain materials other than Fe, Ni, and Co, specific examples of which include Al, Si, S, Sc, Ti, V, Cu, Y, Mo, Rh, Pd, Ag, Sn, Sb, Te, Ba, Ta, W, Re, Au, Bi, La, Ce, Pr, Nd, P, Zn, Zr, Mn, Cr, Nb, Pb, Ca, B, C, N, and O.
• the magnetic particles contain metal atoms other than Fe, Ni, and Co, it is preferable that the particles contain one or more types selected from the group consisting of Si, Cr, B, and Mo.
• the magnetic particles include Fe-Co based alloys (preferably permendur), Fe-Ni based alloys (e.g. permalloy), Fe-Zr based alloys, Fe-Mn based alloys, Fe-Si based alloys, Fe-Al based alloys, Ni-Mo based alloys (preferably supermalloy), Fe-Ni-Co based alloys, Fe-Si-Cr based alloys, Fe-Si-B based alloys, Fe-Si-Al based alloys (preferably sendust), Fe-Si-B-C based alloys, Fe-Si- Examples of the alloy include B-Cr alloys, Fe-Si-B-Cr-C alloys, Fe-Co-Si-B alloys, Fe-Si-B-Nb alloys, Fe nanocrystalline alloys, Fe-based amorphous alloys, and Co-based amorphous alloys, as well as ferrites such as spinel ferrites (preferably Ni-Zn ferrites and
• the alloys may be amorphous.
• preferred hexagonal ferrites include magnetoplumbite-type hexagonal ferrites in which a part of the iron atoms of the hexagonal ferrite is replaced by an aluminum atom.Furthermore, Ba-Fe-Al alloys, Ca-Fe-Al alloys, or Pb-Fe-Al alloys in which a part of the alloy is replaced by Ba, Ca, or Pb are more preferred from the viewpoint of electromagnetic wave absorption in the high frequency band.
• the magnetic particles may be used alone or in combination of two or more kinds.
• the magnetic particles may have a surface layer on the surface thereof, and by the magnetic particles having a surface layer in this manner, the magnetic particles can be endowed with a function according to the material of the surface layer.
• the surface layer may be an inorganic layer or an organic layer.
• the thickness of the surface layer is not particularly limited, but a thickness of 3 to 1000 nm is preferred in order to maximize the functionality of the surface layer.
• the average primary particle size of the magnetic particles is preferably 20 to 1000 nm, and more preferably 20 to 500 nm from the viewpoints of dispersion in the composition and pattern resolution.
• the particle diameter of the primary particles of the magnetic particles is measured by taking a photograph of the magnetic particles at a magnification of 100,000 times using a transmission electron microscope, printing the photograph on photographic paper to a total magnification of 500,000 times, tracing the outline of the particle (primary particle) with a digitizer, and calculating the diameter of a circle with the same area as the traced area (circular area diameter).
• the primary particle refers to an independent particle without aggregation.
• the photograph using a transmission electron microscope is performed by a direct method using a transmission electron microscope at an acceleration voltage of 300 kV.
• the observation and measurement using a transmission electron microscope can be performed, for example, using a Hitachi transmission electron microscope H-9000 type and Carl Zeiss image analysis software KS-400.
• the particle diameters of the primary particles of at least 100 magnetic particles measured above are arithmetically averaged to calculate the average primary particle diameter.
• the shape of the magnetic particles is not particularly limited, and may be plate-like, elliptical, spherical, or irregular.
• the content of the magnetic particles is preferably from 20 to 99% by mass, more preferably from 20 to 80% by mass, and even more preferably from 20 to 60% by mass, based on the total mass of the composition.
• the content of the magnetic particles is preferably from 20 to 99% by mass, more preferably from 30 to 80% by mass, and even more preferably from 30 to 70% by mass, based on the total solid content of the composition.
• the polymerizable compound is a compound having a polymerizable group (photopolymerizable compound), and examples thereof include a compound having a group containing an ethylenically unsaturated bond (hereinafter also simply referred to as an "ethylenically unsaturated group") and a compound having an epoxy group and/or an oxetanyl group, with a compound having an ethylenically unsaturated group being preferred.
• the composition preferably contains a low molecular weight compound containing an ethylenically unsaturated group as a polymerizable compound.
• the polymerizable compound is preferably a compound containing one or more ethylenically unsaturated bonds, more preferably a compound containing two or more ethylenically unsaturated bonds, even more preferably a compound containing three or more ethylenically unsaturated bonds, and particularly preferably a compound containing five or more ethylenically unsaturated bonds.
• the upper limit is, for example, 15 or less.
• Examples of the ethylenically unsaturated group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group.
• the polymerizable compound for example, the compounds described in paragraph 0050 of JP-A-2008-260927 and paragraph 0040 of JP-A-2015-068893 can be used, the contents of which are incorporated herein by reference.
• the polymerizable compound may be in any chemical form, such as a monomer, a prepolymer, an oligomer, a mixture thereof, or a polymer thereof.
• the polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, and more preferably a 3- to 6-functional (meth)acrylate compound.
• the polymerizable compound is also preferably a compound that contains one or more ethylenically unsaturated groups and has a boiling point of 100°C or higher under normal pressure.
• the compounds described in paragraphs 0227 of JP2013-029760A and paragraphs 0254 to 0257 of JP2008-292970A can be taken into consideration, the contents of which are incorporated herein by reference.
• the above polymerizable compounds are preferably dipentaerythritol triacrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., and A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which the (meth)acryloyl group is mediated by an ethylene glycol residue or a propylene glycol residue (for example, SR454, SR499, commercially available
• NK Ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
• KAYARAD RP-1040 KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060, and KAYARAD DPEA-12 (all trade names, manufactured by Nippon Kayaku Co., Ltd.), etc. may also be used.
• the polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group.
• the polymerizable compound containing an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably a polymerizable compound in which an acid group is provided by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride, and even more preferably a compound in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol in the ester.
• the acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mgKOH/g, and more preferably 5 to 30 mgKOH/g. If the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the developing and dissolving properties are good, and if it is 40 mgKOH/g or less, it is advantageous in terms of production and/or handling. Furthermore, the photopolymerization performance is good and the curing properties are excellent.
• the polymerizable compound is a compound containing a caprolactone structure.
• the compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule, and examples thereof include ⁇ -caprolactone-modified polyfunctional (meth)acrylates obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, or trimethylolmelamine with (meth)acrylic acid and ⁇ -caprolactone.
• a compound containing a caprolactone structure represented by the following formula (Z-1) is preferred.
• R 1 represents a hydrogen atom or a methyl group
• m represents the number 1 or 2
• "*" represents a bond
• R 1 represents a hydrogen atom or a methyl group
• "*" represents a bond
• the above polymerizable compound may also be a compound represented by the following formula (Z-4) or (Z-5).
• E represents -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)-, y represents an integer of 0 to 10, and X represents a (meth)acryloyl group, a hydrogen atom, or a carboxylic acid group.
• the total number of (meth)acryloyl groups is 3 or 4; m represents an integer of 0 to 10; the sum of the m's is an integer of 0 to 40.
• the total number of (meth)acryloyl groups is 5 or 6; n represents an integer of 0 to 10; and the sum of the n's is an integer of 0 to 60.
• n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
• the sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12.
• the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
• preferred are those in which all six Xs in formula (Z-5) are acryloyl groups, and those in formula (Z-5) that are a mixture of a compound in which all six Xs are acryloyl groups and a compound in which at least one of the six Xs is a hydrogen atom.
• Such a configuration can further improve the developability.
• the total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
• pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferred.
• the polymerizable compound may contain a cardo skeleton.
• the above-mentioned polymerizable compound containing a cardo skeleton the above-mentioned polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable.
• the content of the ethylenically unsaturated group in the polymerizable compound is preferably 5.0 mmol/g or more. There is no particular upper limit, but it is generally 20.0 mmol/g or less.
• the content of the polymerizable compound in the composition is not particularly limited, but is preferably from 1 to 40% by mass, more preferably from 5 to 30% by mass, and even more preferably from 10 to 25% by mass, based on the total mass of the composition.
• the content of the polymerizable compound in the composition is not particularly limited, but is preferably from 1 to 40% by mass, more preferably from 5 to 30% by mass, and even more preferably from 10 to 25% by mass, based on the total solid content of the composition.
• the composition may contain materials other than the magnetic particles and polymerizable compound described above.
• the composition may include a resin.
• the resin include (meth)acrylic resin, epoxy resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and phenoxy resin. These resins may be used alone or in combination of two or more.
• One preferred embodiment of the resin is a resin having an unsaturated double bond (for example, an ethylenically unsaturated double bond) and a polymerizable group such as an epoxy group or an oxetanyl group.
• One of the preferred embodiments of the resin is a resin having an acid group, a basic group, or an amide group, which is likely to function as a dispersant for dispersing magnetic particles.
• the acid group include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxyl group, with the carboxy group being preferred.
• Examples of basic groups include amino groups (groups in which one hydrogen atom has been removed from ammonia, primary amines, or secondary amines) and imino groups.
• the resin preferably has a carboxy group or an amide group.
• the acid value of the resin is preferably 10 to 500 mg KOH/g, and more preferably 30 to 400 mg KOH/g.
• the resin it is preferable to use a resin that has improved dispersibility in the composition and a solubility in the solvent of 10 g/L or more, and it is more preferable to use a resin that has a solubility in the solvent of 20 g/L or more.
• the upper limit of the solubility of the resin in the solvent is preferably 2000 g/L or less, and more preferably 1000 g/L or less.
• the solubility of a resin in a solvent means the amount (g) of the resin dissolved in 1 L of the solvent at 25°C.
• the content of the resin is preferably from 0.1 to 40% by mass, more preferably from 1 to 30% by mass, and even more preferably from 10 to 30% by mass, based on the total mass of the composition.
• the content of the resin is preferably from 0.1 to 40% by mass, more preferably from 1 to 35% by mass, and further preferably from 10 to 35% by mass, based on the total solid content of the composition.
• One of the preferred forms of resin is a resin that functions as a dispersant to disperse magnetic particles in the composition (hereinafter, also referred to as a "dispersing resin").
• a dispersing resin By using a dispersing resin, the effects of the present invention are more excellent.
• the dispersing resin may be a resin having a repeating unit containing a graft chain (hereinafter, also referred to as "resin A"). However, resin A may be used for purposes other than functioning as a dispersing agent.
• the content of resin A is preferably from 0.1 to 40 mass %, more preferably from 0.5 to 35 mass %, and even more preferably from 1 to 35 mass %, relative to the total mass of the composition.
• the content of resin A is preferably from 0.1 to 40 mass %, more preferably from 0.5 to 35 mass %, and even more preferably from 1 to 35 mass %, based on the solid content of the composition.
• the graft chain preferably has an atomic number excluding hydrogen atoms of 40 to 10,000, more preferably an atomic number excluding hydrogen atoms of 50 to 2,000, and even more preferably an atomic number excluding hydrogen atoms of 60 to 500.
• the graft chain refers to a chain extending from the root of the main chain (an atom attached to the main chain in a group branching from the main chain) to the end of the group branching from the main chain.
• the graft chain preferably contains a polymer structure, and examples of such a polymer structure include a poly(meth)acrylate structure (e.g., a poly(meth)acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, and a polyether structure.
• a poly(meth)acrylate structure e.g., a poly(meth)acrylic structure
• the graft chain is preferably a graft chain containing at least one structure selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylate structure, and more preferably a graft chain containing at least one of a polyester structure and a polyether structure.
• Resin A may be a resin obtained by using a macromonomer containing a graft chain (a monomer having a polymer structure and bonding to a main chain to form a graft chain).
• the macromonomer containing a graft chain (a monomer having a polymer structure and bonding to a main chain to form a graft chain) is not particularly limited, but a macromonomer containing a reactive double bond group can be preferably used.
• AA-6, AA-10, AB-6, AS-6, AN-6, AW-6, AA-714, AY-707, AY-714, AK-5, AK-30, and AK-32 all trade names, manufactured by Toagosei Co., Ltd.
• Blemmer PP-100, Blemmer PP-500, Blemmer PP-800, Blemmer PP-1000, Blemmer 55-PET-800, Blemmer PME-4000, Blemmer PSE-400, Blemmer PSE-1300, and Blemmer 43PAPE-600B all trade names, manufactured by NOF Corporation.
• Resin A preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or linear polyester, more preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and linear polyester, and further preferably contains at least one structure selected from the group consisting of polymethyl acrylate structure, polymethyl methacrylate structure, polycaprolactone structure, and polyvalerolactone structure. Resin A may contain one of the above structures alone, or may contain a plurality of these structures.
• the polycaprolactone structure refers to a structure containing a ring-opened ⁇ -caprolactone structure as a repeating unit
• the polyvalerolactone structure refers to a structure containing a ring-opened ⁇ -valerolactone structure as a repeating unit.
• the above-mentioned polycaprolactone structure can be introduced into resin A. Furthermore, when resin A contains repeating units in which j and k are 4 in formula (1) described below and formula (2) described below, the above-mentioned polyvalerolactone structure can be introduced into the resin.
• the resin A contains a repeating unit in which X5 is a hydrogen atom and R4 is a methyl group in the formula (4) described below, the above-mentioned polymethyl acrylate structure can be introduced into the resin A.
• the above-mentioned polymethyl methacrylate structure can be introduced into the resin A.
• Resin A preferably contains a repeating unit represented by any one of the following formulas (1) to (4) as a repeating unit containing a graft chain, and more preferably contains a repeating unit represented by any one of the following formulas (1A), (2A), (3A), (3B), and (4).
• W 1 , W 2 , W 3 and W 4 each independently represent an oxygen atom or NH.
• W 1 , W 2 , W 3 and W 4 are preferably an oxygen atom.
• X1 , X2 , X3 , X4 , and X5 each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of synthesis constraints, X1 , X2 , X3 , X4 , and X5 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms), more preferably a hydrogen atom or a methyl group, and further preferably a methyl group.
• Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly restricted in structure.
• Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following linking groups (Y-1) to (Y-21).
• a and B respectively represent the bonding sites with the left terminal group and the right terminal group in formulas (1) to (4).
• (Y-2) or (Y-13) is more preferred from the viewpoint of ease of synthesis.
• Z 1 , Z 2 , Z 3 , and Z 4 each independently represent an organic group.
• the structure of the organic group is not particularly limited, but specific examples include an alkyl group, an alkyl group containing -O-, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group.
• the above-mentioned substituents may be further substituted with a substituent (e.g., a hydroxyl group, a (meth)acryloyloxy group, etc.).
• each is more preferably an alkyl group or alkoxy group having 5 to 24 carbon atoms, and among these, each is particularly preferably a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms.
• the alkyl group contained in the alkoxy group may be linear, branched, or cyclic.
• n, m, p, and q each independently represent an integer of 1 to 500.
• j and k each independently represent an integer of 2 to 8.
• j and k are preferably an integer of 4 to 6, and more preferably 5.
• n and m are preferably integers of 10 or more, and more preferably integers of 20 or more.
• resin A contains a polycaprolactone structure and a polyvalerolactone structure
• the sum of the repeating number of the polycaprolactone structure and the repeating number of the polyvalerolactone structure is preferably an integer of 10 or more, and more preferably an integer of 20 or more.
• R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3's may be the same or different.
• R 4 represents a hydrogen atom or a monovalent organic group, and the structure of this monovalent organic group is not particularly limited. R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group.
• the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 20 carbon atoms, and even more preferably a linear alkyl group having 1 to 6 carbon atoms.
• X 5 and R 4 present in the graft chain may be the same or different from each other.
• Resin A may contain repeating units having two or more different structures, including a graft chain. That is, the molecule of resin A may contain repeating units represented by formulas (1) to (4) having structures different from one another, and when n, m, p, and q in formulas (1) to (4) each represent an integer of 2 or more, in formulas (1) and (2), the side chain may contain structures in which j and k are different from one another, and in formulas (3) and (4), the plurality of R 3 , R 4 , and X 5 present in the molecule may be the same as or different from one another.
• the repeating unit represented by formula (1) is more preferably a repeating unit represented by the following formula (1A).
• the repeating unit represented by formula (2) is more preferably a repeating unit represented by formula (2A) below.
• X1 , Y1 , Z1 , and n have the same meanings as X1 , Y1 , Z1 , and n in formula (1), and the preferred ranges are also the same.
• X2 , Y2 , Z2 , and m have the same meanings as X2 , Y2 , Z2 , and m in formula (2), and the preferred ranges are also the same.
• the repeating unit represented by formula (3) is more preferably a repeating unit represented by the following formula (3A) or formula (3B).
• X 3 , Y 3 , Z 3 and p have the same meanings as X 3 , Y 3 , Z 3 and p in formula (3), and the preferred ranges are also the same.
• resin A contains a repeating unit represented by formula (1A) as a repeating unit containing a graft chain.
• resin A contains a repeating unit containing a polyalkyleneimine structure and a polyester structure.
• the repeating unit containing a polyalkyleneimine structure and a polyester structure preferably contains a polyalkyleneimine structure in the main chain and a polyester structure as a graft chain.
• the polyalkyleneimine structure is a polymerized structure containing two or more identical or different alkyleneimine chains.
• Specific examples of the alkyleneimine chain include alkyleneimine chains represented by the following formula (4A) and formula (4B).
• R x1 and R x2 each independently represent a hydrogen atom or an alkyl group.
• a 1 represents an integer of 2 or more.
• * 1 represents a bonding position with a polyester chain, an adjacent alkyleneimine chain, or a hydrogen atom or a substituent.
• R x3 and R x4 each independently represent a hydrogen atom or an alkyl group.
• a2 represents an integer of 2 or more.
• the alkyleneimine chain represented by formula (4B) is bonded to a polyester chain having an anionic group by forming a salt crosslinking group between N + shown in formula (4B) and the anionic group contained in the polyester chain.
• * in formula (4A) and formula (4B), and * 2 in formula (4B) each independently represent a position at which the group is bonded to the adjacent alkyleneimine chain, or a hydrogen atom or a substituent.
• * in formula (4A) and formula (4B) preferably represents the position at which the alkyleneimine chain is bonded to the adjacent alkyleneimine chain.
• R X1 and R X2 in formula (4A), and R X3 and R X4 in formula (4B) each independently represent a hydrogen atom or an alkyl group.
• the alkyl group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms.
• R 1 X1 and R 1 X2 are both a hydrogen atom.
• R 1 X3 and R 1 X4 are both a hydrogen atom.
• a1 in formula (4A) and a2 in formula (4B) are integers of 2 or more.
• the upper limit is preferably 10 or less, more preferably 6 or less, even more preferably 4 or less, still more preferably 2 or 3, and particularly preferably 2.
• * represents the bonding position to the adjacent alkyleneimine chain, or to a hydrogen atom or a substituent.
• substituent include an alkyl group (for example, an alkyl group having 1 to 6 carbon atoms), etc.
• a polyester chain may be bonded as the substituent.
• the alkyleneimine chain represented by formula (4A) is preferably linked to the polyester chain at the position * 1 described above. Specifically, the carbonyl carbon in the polyester chain is preferably bonded at the position * 1 described above.
• the polyester chain may be represented by the following formula (5A).
• the polyester chain contains an anion (preferably an oxygen anion O ⁇ ), and that this anion and N + in formula (4B) form a salt bridging group.
• An example of such a polyester chain is a polyester chain represented by the following formula (5B).
• L X1 in formula (5A) and L X2 in formula (5B) each independently represent a divalent linking group, preferably an alkylene group having 3 to 30 carbon atoms.
• b 11 in formula (5A) and b 21 in formula (5B) each independently represent an integer of 2 or more, with the upper limit being, for example, 200 or less.
• b 12 in formula (5A) and b 22 in formula (5B) each independently represent 0 or 1.
• X A in formula (5A) and X B in formula (5B) each independently represent a hydrogen atom or a substituent.
• substituents include an alkyl group, an alkoxy group, a polyalkyleneoxyalkyl group, and an aryl group.
• the number of carbon atoms in the alkyl group (which may be linear, branched, or cyclic) and the alkyl group contained in the alkoxy group (which may be linear, branched, or cyclic) is preferably 1 to 30, and more preferably 1 to 10.
• the alkyl group may further have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom).
• a polyalkyleneoxyalkyl group is a substituent represented by R X6 (OR X7 ) p (O) q -, in which R X6 represents an alkyl group, R X7 represents an alkylene group, p represents an integer of 2 or more, and q represents 0 or 1.
• the alkyl group represented by R X6 has the same meaning as the alkyl group represented by X A.
• the alkylene group represented by R X7 includes a group in which one hydrogen atom has been removed from the alkyl group represented by X A.
• p is an integer of 2 or more, and its upper limit is, for example, 10 or less, and preferably 5 or less.
• the aryl group includes, for example, an aryl group having 6 to 24 carbon atoms (which may be either monocyclic or polycyclic).
• the aryl group may further have a substituent, and examples of the substituent include an alkyl group, a halogen atom, and a cyano group.
• the polyester chain is preferably a ring-opened lactone such as ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, enantholactone, ⁇ -butyrolactone, ⁇ -hexanolactone, ⁇ -octanolactone, ⁇ -hexalanolactone, ⁇ -octanolactone, ⁇ -dodecanolactone, ⁇ -methyl- ⁇ -butyrolactone, or lactide (which may be either the L-form or the D-form), and more preferably a ring-opened ⁇ -caprolactone or ⁇ -valerolactone structure.
• lactide which may be either the L-form or the D-form
• the repeating units containing the polyalkyleneimine structure and polyester structure can be synthesized according to the synthesis method described in Japanese Patent No. 5923557.
• the content of repeating units including graft chains, calculated by mass, is preferably 2 to 100 mass% relative to the total mass of resin A, more preferably 2 to 90 mass%, and even more preferably 5 to 30 mass%.
• Hydrophobic Repeating Unit Resin A may also contain a hydrophobic repeating unit different from the repeating unit containing a graft chain (i.e., not corresponding to the repeating unit containing a graft chain).
• the hydrophobic repeating unit is a repeating unit that does not have an acid group (e.g., a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).
• the hydrophobic repeating unit is preferably a repeating unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, and more preferably a repeating unit derived from a compound having a ClogP value of 1.2 to 8.
• the ClogP value is a value calculated by the program "CLOGP” available from Daylight Chemical Information System, Inc. This program provides a "calculated logP” value calculated by the fragment approach of Hansch and Leo (see the following literature).
• the fragment approach is based on the chemical structure of a compound, and divides the chemical structure into partial structures (fragments), and estimates the logP value of the compound by summing up the logP contributions assigned to the fragments. Details are described in the following literature.
• the ClogP value calculated by the program CLOGP v4.82 is used.
• A. J. Leo Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds.
• Log P means the common logarithm of the partition coefficient P, which is a physical property that quantitatively represents how an organic compound is distributed in equilibrium between a two-phase system of oil (generally 1-octanol) and water, and is expressed by the following formula.
• logP log(Coil/Coil)
• Coil represents the molar concentration of the compound in the oil phase
• Cwater represents the molar concentration of the compound in the water phase.
• resin A contains, as a hydrophobic repeating unit, one or more repeating units selected from repeating units derived from monomers represented by the following formulas (i) to (iii).
• R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, etc.).
• R 1 , R 2 , and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
• X represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.
• L is a single bond or a divalent linking group.
• the divalent linking group include a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (e.g., an arylene group, and a substituted arylene group), a divalent heterocyclic group, an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR 31 -, where R 31 is an aliphatic group, an aromatic group, or a heterocyclic group), a carbonyl group (-CO-), and combinations thereof.
• a divalent aliphatic group e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkeny
• L is preferably a single bond, an alkylene group, or a divalent linking group containing an oxyalkylene structure.
• the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
• L may also contain a polyoxyalkylene structure containing two or more repeated oxyalkylene structures.
• the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
• the polyoxyethylene structure is represented by -(OCH 2 CH 2 ) n -, where n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.
• Z includes aliphatic groups (e.g., alkyl groups, substituted alkyl groups, unsaturated alkyl groups, substituted unsaturated alkyl groups), aromatic groups (e.g., aryl groups, substituted aryl groups, arylene groups, substituted arylene groups), heterocyclic groups, and combinations thereof. These groups may contain an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR 31 -, where R 31 is an aliphatic group, an aromatic group, or a heterocyclic group), or a carbonyl group (-CO-).
• aliphatic groups e.g., alkyl groups, substituted alkyl groups, unsaturated alkyl groups, substituted unsaturated alkyl groups
• aromatic groups e.g., aryl groups, substituted aryl groups, arylene groups, substituted arylene groups
• heterocyclic groups e.g.,
• R 4 , R 5 , and R 6 each independently represent a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, etc.), Z, or L-Z, where L and Z have the same meaning as the above groups.
• R 4 , R 5 , and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
• a compound in which R 1 , R 2 , and R 3 are hydrogen atoms or methyl groups, L is a single bond or a divalent linking group containing an alkylene group or an oxyalkylene structure, X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferred.
• a compound in which R1 is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferred.
• R4 , R5 , and R6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferred.
• the content of hydrophobic repeating units is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass, relative to the total mass of resin A, calculated by mass.
• Resin A may have a functional group capable of forming an interaction with magnetic particles. It is preferable that resin A further contains a repeating unit containing a functional group capable of forming an interaction with the magnetic particles. Examples of functional groups capable of forming interactions with magnetic particles include acid groups, basic groups, coordinating groups, and reactive functional groups. When Resin A contains an acid group, a basic group, a coordinating group, or a reactive functional group, it preferably contains a repeating unit containing an acid group, a repeating unit containing a basic group, a repeating unit containing a coordinating group, or a repeating unit having a reactive functional group, respectively.
• the repeating unit containing an alkali-soluble group as an acid group may be the same repeating unit as the repeating unit containing the graft chain described above, or a different repeating unit, but the repeating unit containing an alkali-soluble group as an acid group is a repeating unit different from the hydrophobic repeating unit described above (i.e., it does not correspond to the hydrophobic repeating unit described above).
• Examples of the acid group which is a functional group capable of forming an interaction with the magnetic particles, include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and at least one of the carboxylic acid group, the sulfonic acid group, and the phosphoric acid group is preferred, and the carboxylic acid group is more preferred.
• the carboxylic acid group has a good adsorption force to the magnetic particles and is highly dispersible. That is, it is preferable that resin A further contains a repeating unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
• Resin A may have one or more types of repeating units containing an acid group.
• the content thereof is preferably from 5 to 80% by mass, and more preferably from 10 to 60% by mass, based on the total mass of the resin A, in terms of mass.
• Examples of basic groups that are functional groups capable of forming an interaction with magnetic particles include primary amino groups, secondary amino groups, tertiary amino groups, heterocycles containing N atoms, and amide groups, and a preferred basic group is a tertiary amino group because of its good adsorption to magnetic particles and high dispersibility.
• Resin A may contain one or more of these basic groups.
• the content thereof is preferably from 0.01 to 50% by mass, and more preferably from 0.01 to 30% by mass, based on the total mass of the resin A, in terms of mass.
• Examples of functional groups that can form an interaction with magnetic particles include an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, and an acid chloride.
• a preferred functional group is an acetylacetoxy group, which has good adsorption power to magnetic particles and high dispersibility of magnetic particles.
• Resin A may have one or more of these groups. When resin A contains a repeating unit containing a coordinating group or a repeating unit containing a reactive functional group, the content of these units, calculated on a mass basis, is preferably 10 to 80 mass%, and more preferably 20 to 60 mass%, relative to the total mass of resin A.
• the resin A contains functional groups capable of forming interactions with magnetic particles other than the graft chains
• these functional groups are introduced as long as it contains functional groups capable of forming interactions with the various magnetic particles described above.
• the resin contained in the composition contains one or more types of repeating units selected from repeating units derived from monomers represented by the following formulas (iv) to (vi).
• R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, etc.).
• R 11 , R 12 and R 13 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
• R 12 and R 13 are further preferably a hydrogen atom.
• X 1 in formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
• Y in formula (v) represents a methine group or a nitrogen atom.
• L1 in formulas (iv) to (v) represents a single bond or a divalent linking group.
• the definition of the divalent linking group is the same as the definition of the divalent linking group represented by L in formula (i) above.
• L 1 is preferably a single bond, an alkylene group, or a divalent linking group containing an oxyalkylene structure.
• the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
• L 1 may also contain a polyoxyalkylene structure containing two or more repeated oxyalkylene structures.
• the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
• the polyoxyethylene structure is represented by -(OCH 2 CH 2 ) n -, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
• Z1 represents a functional group capable of forming an interaction with the magnetic particles other than the graft chain, and is preferably a carboxylic acid group or a tertiary amino group, more preferably a carboxylic acid group.
• R 14 , R 15 , and R 16 each independently represent a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, etc.), -Z 1 , or L 1 -Z 1.
• L 1 and Z 1 have the same meaning as L 1 and Z 1 above, and preferred examples are also the same.
• R 14 , R 15 , and R 16 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.
• a compound in which R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, L 1 is an alkylene group or a divalent linking group containing an oxyalkylene structure, X 1 is an oxygen atom or an imino group, and Z 1 is a carboxylic acid group is preferred.
• a compound in which R 11 is a hydrogen atom or a methyl group, L 1 is an alkylene group, Z 1 is a carboxylic acid group, and Y is a methine group is preferable.
• a compound in which R 14 , R 15 and R 16 each independently represent a hydrogen atom or a methyl group, and Z 1 is a carboxylic acid group is preferable.
• the content of the repeating unit containing a functional group capable of forming an interaction with the magnetic particles is, in terms of the interaction with the magnetic particles, stability over time, and permeability to the developer, preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, and even more preferably 10 to 70% by mass, relative to the total mass of resin A.
• Ethylenically Unsaturated Group Resin A may contain an ethylenically unsaturated group.
• the ethylenically unsaturated group is not particularly limited, but examples thereof include a (meth)acryloyl group, a vinyl group, and a styryl group, with a (meth)acryloyl group being preferred.
• Resin A preferably contains a repeating unit containing an ethylenically unsaturated group in the side chain, and more preferably contains a repeating unit containing an ethylenically unsaturated group in the side chain and derived from a (meth)acrylate (hereinafter also referred to as a "(meth)acrylic repeating unit containing an ethylenically unsaturated group in the side chain").
• the (meth)acrylic repeating unit containing an ethylenically unsaturated group in the side chain can be obtained, for example, by subjecting an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to an addition reaction of the carboxylic acid group in the resin A containing a (meth)acrylic repeating unit containing a carboxylic acid group.
• an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to an addition reaction of the carboxylic acid group in the resin A containing a (meth)acrylic repeating unit containing a carboxylic acid group.
• resin A contains a repeating unit containing an ethylenically unsaturated group
• the content thereof, calculated by mass is preferably 30 to 70 mass% and more preferably 40 to 60 mass% relative to the total mass of resin A.
• resin A may further have other repeating units having various functions different from the repeating units containing a graft chain, the hydrophobic repeating units, and the repeating units containing a functional group capable of forming an interaction with the magnetic particles, as long as the effects of the present invention are not impaired.
• Examples of such other repeating units include repeating units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles.
• Resin A may contain one or more of these other repeating units, and the content thereof, calculated on a mass basis, is preferably from 0 to 80 mass %, more preferably from 10 to 60 mass %, based on the total mass of resin A.
• the acid value of Resin A is not particularly limited, but is, for example, preferably 0 to 400 mgKOH/g, more preferably 10 to 350 mgKOH/g, still more preferably 30 to 300 mgKOH/g, and particularly preferably 50 to 200 mgKOH/g. If the acid value of resin A is 50 mgKOH/g or more, the sedimentation stability of the magnetic particles can be further improved.
• the acid value can be calculated, for example, from the average content of acid groups in a compound.
• a resin having a desired acid value can be obtained by changing the content of repeating units containing acid groups in the resin.
• the weight average molecular weight of the resin A is not particularly limited, but is, for example, preferably 3,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, and particularly preferably 6,000 or more.
• the upper limit is, for example, preferably 300,000 or less, more preferably 200,000 or less, even more preferably 100,000 or less, and particularly preferably 50,000 or less.
• Resin A can be synthesized based on a known method.
• the resin may contain an alkali-soluble resin.
• the alkali-soluble resin means a resin containing a group that promotes alkali solubility (an alkali-soluble group, for example, an acid group such as a carboxylic acid group), and means a resin different from the resin A already described.
• alkali-soluble resins include resins that contain at least one alkali-soluble group in the molecule, such as polyhydroxystyrene resins, polysiloxane resins, (meth)acrylic resins, (meth)acrylamide resins, (meth)acrylic/(meth)acrylamide copolymers, epoxy resins, and polyimide resins.
• alkali-soluble resins include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds.
• the unsaturated carboxylic acid is not particularly limited, and examples thereof include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and vinylacetic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, or acid anhydrides thereof; and polyvalent carboxylic acid monoesters such as mono(2-(meth)acryloyloxyethyl)phthalate.
• copolymerizable ethylenically unsaturated compounds examples include methyl (meth)acrylate.
• the compounds described in paragraph 0027 of JP 2010-097210 A and paragraphs 0036 to 0037 of JP 2015-068893 A can also be used, and the contents of the above are incorporated herein by reference.
• a copolymerizable ethylenically unsaturated compound having an ethylenically unsaturated group in a side chain may be used in combination.
• the alkali-soluble resin may contain a repeating unit having an ethylenically unsaturated group in a side chain.
• the ethylenically unsaturated group contained in the side chain is preferably a (meth)acrylic acid group.
• a repeating unit containing an ethylenically unsaturated group in a side chain can be obtained, for example, by subjecting a carboxylic acid group of a (meth)acrylic repeating unit containing a carboxylic acid group to an addition reaction with an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group.
• the alkali-soluble resin is also preferably an alkali-soluble resin containing a curable group.
• the curable group include, but are not limited to, ethylenically unsaturated groups (e.g., (meth)acryloyl groups, vinyl groups, styryl groups, etc.) and cyclic ether groups (e.g., epoxy groups, oxetanyl groups, etc.).
• the curable group is preferably an ethylenically unsaturated group, and more preferably a (meth)acryloyl group, in terms of the ability to control polymerization by radical reaction.
• the alkali-soluble resin containing a curable group is preferably an alkali-soluble resin having a curable group in a side chain, etc.
• Examples of the alkali-soluble resin containing a curable group include Dianaru NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer.
• Diamond Shamrock Co., Ltd. shows a variety of materials that are used for the following purposes: Diamond Shamrock Co., Ltd., Viscoat R-264, KS Resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (e.g., ACA230AA), Plaxel CF200 series (both manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel Allnex Corporation), and Acricur RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).
• Cyclomer P series e.g., ACA230AA
• Plaxel CF200 series both manufactured by Daicel Corporation
• Ebecryl 3800 manufactured by Daicel Allnex Corporation
• Acricur RD-F8 manufactured by Nippon Shokubai Co., Ltd.
• a polyimide precursor is a resin obtained by subjecting a compound containing an acid anhydride group and a diamine compound to an addition polymerization reaction at 40 to 100°C.
• the alkali-soluble resin a copolymer of benzyl (meth)acrylate/(meth)acrylic acid/if necessary, other addition-polymerizable vinyl monomers and a copolymer of allyl (meth)acrylate/(meth)acrylic acid/if necessary, other addition-polymerizable vinyl monomers are preferred, as they have an excellent balance of film strength, sensitivity, and developability.
• the other addition-polymerizable vinyl monomers may be used alone or in combination of two or more kinds.
• the copolymer preferably has a curable group, and more preferably contains an ethylenically unsaturated group such as a (meth)acryloyl group.
• a curable group may be introduced into the copolymer by using a monomer having a curable group as the other addition-polymerizable vinyl monomer.
• a curable group preferably an ethylenically unsaturated group such as a (meth)acryloyl group
• a curable group may be introduced into a part or all of one or more of the units derived from (meth)acrylic acid and/or the units derived from the other addition-polymerizable vinyl monomer in the copolymer.
• the other addition-polymerizable vinyl monomers include methyl (meth)acrylate, styrene-based monomers (such as hydroxystyrene), and ether dimers.
• the ether dimer include a compound represented by the following general formula (ED1) and a compound represented by the following general formula (ED2).
• R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms.
• R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. Specific examples of general formula (ED2) can be found in JP 2010-168539 A.
• ether dimers can be found in, for example, paragraph 0317 of JP 2013-029760 A, the contents of which are incorporated herein by reference.
• the ether dimer may be of only one type, or of two or more types.
• the acid value of the alkali-soluble resin is not particularly limited, but is preferably 30 to 500 mg KOH/g, and more preferably 50 to 200 mg KOH/g or more.
• the content of the alkali-soluble resin is preferably 0.1 to 40 mass %, more preferably 0.5 to 30 mass %, and even more preferably 1 to 20 mass %, based on the total mass of the composition.
• the content of resin A is preferably from 0.1 to 40 mass %, more preferably from 0.5 to 30 mass %, and even more preferably from 1 to 20 mass %, based on the solid content of the composition.
• the composition may contain a solvent, such as water or an organic solvent, with the organic solvent being preferred.
• a solvent such as water or an organic solvent
• the boiling point of the solvent is preferably from 100 to 400° C., more preferably from 150 to 300° C., and even more preferably from 170 to 250° C.
• the boiling point means the standard boiling point, unless otherwise specified.
• organic solvents include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, and ethylene glycol monobutyl ether.
• acetate examples include, but are not limited to, acetate, 1,4-butanediol diacetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethylsulfoxide, ⁇ -butyrolactone, ethyl acetate, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, and ethyl lactate.
• the content of the solvent is preferably 1 to 60 mass %, more preferably 2 to 50 mass %, and even more preferably 3 to 40 mass %, based on the total mass of the composition.
• the composition may include a polymerization initiator.
• the polymerization initiator is not particularly limited, and a known polymerization initiator can be used. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, and a photopolymerization initiator is preferred.
• the polymerization initiator is preferably a so-called radical polymerization initiator.
• the content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.5 to 15 mass %, more preferably 1.0 to 10 mass %, and even more preferably 1.5 to 8.0 mass %, based on the total mass of the composition.
• the content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.5 to 15 mass %, more preferably 1.0 to 15 mass %, and even more preferably 1.5 to 12 mass %, based on the total solid content of the composition.
• Photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, etc.
• halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
• acylphosphine compounds e.g., acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, etc.
• the photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, or a 3-aryl-substituted coumarin compound, more preferably a compound selected from an oxime compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound.
• examples of the photopolymerization initiator include the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A and Japanese Patent No. 6301489 A, and the compounds described in MATERIAL STAGE 37 to 60p, vol. 19, No.
• ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (all manufactured by BASF), etc.
• Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (all manufactured by BASF), etc.
• Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (all manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (all manufactured by BASF), etc.
• Oxime compounds include the compounds described in JP-A-2001-233842, JP-A-2000-080068, JP-A-2006-342166, J. C. S. Perkin II (1979, pp. 1653-1660), and J. C. S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp.
• JP-A-2000-066385 JP-T-2004-534797, JP-A-2006-342166, Compounds described in JP 17-019766 A, compounds described in JP 6065596 A, compounds described in WO 2015/152153 A, compounds described in WO 2017/051680 A, compounds described in JP 2017-198865 A, compounds described in paragraphs 0025 to 0038 of WO 2017/164127 A, compounds described in WO 2013/167515 A, and the like.
• oxime compound examples include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
• an oxime compound having a fluorene ring can also be used.
• Specific examples of oxime compounds having a fluorene ring include the compounds described in JP 2014-137466 A, the compounds described in Japanese Patent No. 6,636,081 A, and the compounds described in Korean Patent Publication No. 10-2016-0109444.
• an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring can also be used.
• Specific examples of such oxime compounds include the compounds described in WO 2013/083505.
• an oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
• oxime compounds having a fluorine atom include the compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and compound (C-3) described in JP-A-2013-164471.
• an oxime compound having a nitro group can be used as the photopolymerization initiator. It is also preferable that the oxime compound having a nitro group is a dimer.
• Specific examples of oxime compounds having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012 and 0070 to 0079 of JP 2014-137466 A, the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 A, and ADEKA ARCLES NCI-831 (manufactured by ADEKA Corporation).
• Oxime compounds having a benzofuran skeleton can also be used as photopolymerization initiators. Specific examples include OE-01 to OE-75 described in WO 2015/036910.
• an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used.
• photopolymerization initiators include the compounds described in WO 2019/088055.
• oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited to these.
• the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
• the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1000 to 300,000, even more preferably 2000 to 300,000, and particularly preferably 5000 to 200,000.
• the molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure using a spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.
• a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photopolymerization initiator.
• two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained.
• the crystallinity is reduced and the solubility in a solvent or the like is improved, so that precipitation is less likely to occur over time, and the stability of the composition over time can be improved.
• bifunctional or trifunctional or higher functional photoradical polymerization initiators include the dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-P-2015/004565, paragraphs 0407 to 0412 of JP-T-2016-532675, and paragraphs 0039 to 0055 of WO-P-2017/033680, compound (E) and compound (G) described in WO-P-2013-522445, and compound (C) described in WO-P-2015-004565, and compound (D) described in WO-P-2015-004565, and compound (E) and compound (D) described in WO-P-2015-004565, ...
• Examples of the photoinitiator include Cmpd1 to 7 described in JP 2016/034963 A, the oxime ester photoinitiator described in paragraph 0007 of JP 2017-523465 A, the photoinitiator described in paragraphs 0020 to 0033 of JP 2017-167399 A, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP 2017-151342 A, and the oxime ester photoinitiator described in Japanese Patent No. 6469669 A.
• the composition may further contain other optional components other than the above-mentioned components.
• optional components for example, surfactants, polymerization inhibitors, antioxidants, sensitizers, co-sensitizers, crosslinking agents (curing agents), curing accelerators, heat curing accelerators, plasticizers, diluents, sensitizers, and rubber components may be mentioned, and further, known additives such as adhesion promoters to the substrate surface and other auxiliaries (for example, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension adjusters, and chain transfer agents) may be added as necessary.
• auxiliaries for example, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension adjusters, and chain transfer agents
• surfactant examples include various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, silicone surfactants, etc.
• surfactant examples include the surfactants described in paragraphs 0238 to 0245 of WO 2015/166779, the contents of which are incorporated herein by reference.
• fluorine-based surfactants include those described in paragraphs 0060 to 0064 of JP 2014-041318 A (corresponding paragraphs 0060 to 0064 of WO 2014/017669 A), those described in paragraphs 0117 to 0132 of JP 2011-132503 A, and those described in JP 2020-008634 A, the contents of which are incorporated herein by reference.
• fluorine-based surfactants include, for example, Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F -558, F-559, F-560, F-561, F-563, F-565, F-568, F-575, F-780, EXP, MFS-330, R-01, R-40, R-40-LM, R-41, R-41-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (and above, DI C Co., Ltd.), Fluorard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068
• an acrylic compound that has a molecular structure with a functional group containing a fluorine atom and that volatilizes the fluorine atom by cleaving the functional group when heated can also be suitably used.
• fluorosurfactants include the Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Business Daily (February 23, 2016)), such as Megafac DS-21.
• fluorosurfactant a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
• fluorosurfactants include the fluorosurfactants described in JP 2016-216602 A, the contents of which are incorporated herein by reference.
• a block polymer can also be used as the fluorosurfactant.
• a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used as the fluorosurfactant.
• the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorosurfactant used in the present invention.
• the weight average molecular weight of the above compounds is preferably 3,000 to 50,000, for example, 14,000. In the above compounds, the percentage indicating the proportion of repeating units is mol%.
• a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can be used.
• Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965A, and Megafac RS-101, RS-102, RS-718K, and RS-72-K manufactured by DIC Corporation.
• the fluorosurfactant the compounds described in paragraphs 0015 to 0158 of JP2015-117327A can be used.
• surfactants described in WO 2020/084854 as a substitute for surfactants having a perfluoroalkyl group having 6 or more carbon atoms.
• m represents 1 or 2
• n represents an integer from 1 to 4
• ⁇ represents 1 or 2
• X ⁇ + represents an ⁇ -valent metal ion, a primary ammonium ion, a secondary ammonium ion, a tertiary ammonium ion, a quaternary ammonium ion, or NH4 + .
• Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid.
• esters examples include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil Co., Ltd.), Olfin E1010, and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).
• Cationic surfactants include tetraalkylammonium salts, alkylamine salts, benzalkonium salts, alkylpyridinium salts, imidazolium salts, etc. Specific examples include dihydroxyethylstearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, stearamidomethylpyridinium chloride, etc.
• Anionic surfactants include dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyletherdisulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium dialkylsulfosuccinate, sodium stearate, sodium oleate, sodium t-octylphenoxyethoxypolyethoxyethyl sulfate, etc.
• silicone surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, and TSF- 4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 (all manufactured by BYK-Chemie), FZ-2122 (manufactured by Dow Toray Co., Ltd.), etc.
• the magnetic particles may be the same as those contained in composition A, and preferred embodiments are also the same.
• the content of the magnetic particles is preferably 20 to 99 mass %, more preferably 25 to 80 mass %, and even more preferably 30 to 60 mass %, based on the total mass of the composition.
• the content of the magnetic particles is preferably from 30 to 99% by mass, more preferably from 30 to 80% by mass, and even more preferably from 40 to 70% by mass, based on the total solid content of the composition.
• the resin may be the same as the resin contained in composition A, and the preferred embodiments are also the same.
• the resin may be a dispersion resin or an alkali-soluble resin.
• As the alkali-soluble resin in composition B phenol novolac resins, cresol novolac resins, alkali-soluble polyimide resins, polybenzoxazole precursors, and the like can also be preferably used.
• the content of the resin is preferably from 0.1 to 40 mass %, more preferably from 1 to 30 mass %, and even more preferably from 10 to 30 mass %, based on the total mass of the composition.
• the content of the resin is preferably from 0.1 to 40 mass %, more preferably from 1 to 35 mass %, and even more preferably from 10 to 35 mass %, based on the total solid content of the composition.
• composition B contains resin A
• the content of resin A is preferably 0.1 to 30 mass %, more preferably 0.5 to 20 mass %, and even more preferably 1 to 10 mass %, based on the total mass of the composition.
• the content of resin A is preferably 0.1 to 30 mass %, more preferably 0.5 to 20 mass %, and even more preferably 1 to 10 mass %, based on the solid content of the composition.
• composition B contains an alkali-soluble resin
• the content of the alkali-soluble resin is preferably 0.1 to 30 mass %, more preferably 1 to 30 mass %, and even more preferably 5 to 30 mass %, based on the total mass of the composition.
• the content of the alkali-soluble resin is preferably 0.1 to 30 mass%, more preferably 1 to 30 mass%, and even more preferably 5 to 30 mass%, based on the total solid content of the composition.
• the solvent may be the same as that contained in composition A, and the preferred embodiments are also the same.
• the content of the solvent is preferably from 1 to 60% by mass, more preferably from 2 to 50% by mass, and even more preferably from 3 to 40% by mass, based on the total mass of the composition.
• Examples of compounds that become alkali-soluble upon irradiation with light include quinone diazide compounds.
• quinone diazide compound compounds known as photosensitizers for positive resist compositions can be used.
• quinone diazide compounds include diazonaphthoquinone (DNQ); ester compounds of 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid with low molecular weight aromatic hydroxy compounds (e.g., 2,3,4-trihydroxybenzophenone, 1,3,5-trihydroxybenzene, 2,3,4,4′-tetrahydroxybenzophenone, 2- and 4-methylphenol, 4,4′-hydroxypropane); naphthoquinone diazide derivatives represented by the formulas (NA), (NB), and (NC); and the like.
• DNQ diazonaphthoquinone
• the content of the compound that is alkali-soluble upon irradiation with light is preferably 1 to 20 mass %, more preferably 1 to 15 mass %, and even more preferably 1 to 10 mass %, based on the total mass of the composition.
• the content of the compound that is alkali-soluble upon irradiation with light is preferably 1 to 20 mass %, more preferably 1 to 15 mass %, and even more preferably 1 to 10 mass %, based on the total solid content of the composition.
• the crosslinking agent can be appropriately selected depending on the type of resin.
• Specific examples of the crosslinking agent include diamines, polyisocyanates, benzoxazines, and resols, and any compound known as a crosslinking agent can be used appropriately.
• the content of the crosslinking agent in the composition B is preferably from 0.1 to 20% by mass, more preferably from 0.1 to 15% by mass, and even more preferably from 1 to 10% by mass, based on the total mass of the composition.
• the content of the crosslinking agent in the composition B is preferably from 0.1 to 20 mass %, more preferably from 0.1 to 15 mass %, and even more preferably from 1 to 10 mass %, based on the solid content of the composition.
• Composition B may further contain other optional components in addition to the components described above.
• other optional components include the same as the other optional components contained in composition A, and preferred embodiments are also the same.
• composition containing magnetic particles [Pattern formation and evaluation (1)] [Preparation of composition containing magnetic particles] The following various components were mixed to prepare a composition containing magnetic particles (magnetic particle-containing composition).
• Magnetic particles (particles A below) 24.86 parts by weight Alkali-soluble resin (resin B1 below) 0.06 parts by weight Dispersant (resin B2 below) 22.38 parts by weight Polymerizable compound (KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)) 17.08 parts by weight of polymerization initiator (compound C below) 6.98 parts by weight of surfactant (KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone surfactant)) 0.06 parts by mass Solvent (PGMEA) 28.58 parts by mass
• Particles A are barium ferrite produced by the following procedure. ⁇ Creation of magnetic particles>> 400.0 g of water kept at a liquid temperature of 35° C. was stirred, and a raw material aqueous solution prepared by dissolving 57.0 g of iron ( III ) chloride hexahydrate [ FeCl3.6H2O ], 25.4 g of barium chloride dihydrate [ BaCl2.2H2O ], and 10.2 g of aluminum chloride hexahydrate [ AlCl3.6H2O ] in 216.0 g of water, and a solution prepared by adding 113.0 g of water to 181.3 g of a 5 mol/L aqueous sodium hydroxide solution were added in their entirety at the same timing at a flow rate of 10 mL/min to the stirred water, to obtain a first liquid.
• the temperature of the first liquid was adjusted to 25° C., and then 39.8 g of a 1 mol/L aqueous sodium hydroxide solution was added while maintaining this temperature to obtain a second liquid.
• the pH of the obtained second liquid was 10.5 ⁇ 0.5.
• the pH was measured using a tabletop pH meter (F-71 manufactured by Horiba, Ltd.).
• the second liquid was stirred for 15 minutes to obtain a liquid containing a precipitate that would become a precursor of magnetoplumbite-type hexagonal ferrite (precursor-containing liquid).
• the precursor-containing liquid was subjected to a centrifugal separation process (rotation speed: 2000 rpm (revolutions per minute), rotation time: 10 minutes) three times, and the resulting precipitate was collected and washed with water.
• the collected precipitate was then dried in an oven at an internal atmospheric temperature of 95° C. for 12 hours to obtain a precursor powder.
• the precursor powder was placed in a muffle furnace, and the temperature inside the furnace was set to 1100° C. in an air atmosphere, and the powder was fired for 4 hours to obtain a sintered block.
• the obtained sintered body was pulverized for 90 seconds using a cutter mill (Wonder Crusher WC-3 manufactured by Osaka Chemical Co., Ltd.) as a pulverizer, with the variable speed dial of the pulverizer set to "5" (rotation speed: approximately 10,000 to 15,000 rpm), to obtain a magnetic powder.
• a cutter mill Wood Crusher WC-3 manufactured by Osaka Chemical Co., Ltd.
• the variable speed dial of the pulverizer set to "5" (rotation speed: approximately 10,000 to 15,000 rpm), to obtain a magnetic powder.
• the crystal structure of the magnetic material constituting each of the magnetic powders was confirmed by X-ray diffraction analysis.
• the measurement device used was a powder X-ray diffraction device, X'Pert Pro, manufactured by PANalytical Co.
• the measurement conditions are as follows: - Measurement conditions - X-ray source: CuK ⁇ ray [wavelength: 1.54 ⁇ (0.154 nm), output: 40 mA, 45 kV] Scan range: 20° ⁇ 2 ⁇ 70° Scan interval: 0.05° Scan speed: 0.75°/min
• X-ray diffraction analysis it was confirmed that the obtained magnetic powder has a magnetoplumbite type crystal structure and is a powder of single-phase magnetoplumbite type hexagonal ferrite containing no crystal structure other than magnetoplumbite type.
• Resin B1 Resin with the following structure (the numbers in each repeating unit in the formula below represent the content (mass%) relative to the total repeating units.)
• Resin B2 Resin with the following structure (in the formula below, a to e represent the content (mol %) of each repeating unit relative to the total repeating units. x and y represent the average number added).
• Compound C Compound with the following structure (oxime ester polymerization initiator)
• Poloxamer 407 (Surfactant/Water-soluble polymer) Poloxamer 407 (Sigma-Aldrich, a compound having a polyethylene oxide structure and a polypropylene oxide structure (corresponding to a water-soluble polymer)) - Marialim SC0505K (manufactured by NOF Corporation, a compound having a polyoxyalkylene group on the side chain (corresponding to a water-soluble polymer)) Dispanol WI-133 (manufactured by NOF Corporation, a compound having a polyoxyalkylene group on the side chain (corresponding to a water-soluble polymer)) - Esreem AD3172M (manufactured by NOF Corporation, a compound having a polyoxyalkylene group on the side chain (corresponding to a water-soluble polymer))
• the magnetic particle-containing composition prepared above was applied onto a silicon wafer to form a coating film, which was then dried at 100° C. for 2 minutes. Next, the coating film was exposed through a mask having a predetermined opening using a USHIO simple exposure device under the condition of 10 mJ/cm 2 . After the exposure, a shower development process was carried out for 60 seconds at 23° C. using a simple developing device (manufactured by Mikasa Co., Ltd.) The developing solution used was CD-2060 manufactured by Fujifilm Electronic Materials Co., Ltd. Immediately after development, a rinsing treatment was carried out by spraying the chemical solution shown in Table 1 for 15 seconds at 23° C.
• a rinsing treatment was carried out by spraying ultrapure water for 15 seconds at 23° C. using a spray rinse nozzle, and finally a spin drying treatment was carried out. Thereafter, a heat treatment (post-bake) was carried out for 5 minutes using a hot plate at 220° C. to obtain a silicon wafer and a laminate having a predetermined negative pattern on the silicon wafer.
• the chemical solutions of the examples are excellent in removing defects on a patterned substrate that includes a substrate and a pattern containing magnetic particles. Furthermore, from the results of the examples, it was confirmed that when the chemical solution contains water; a surfactant containing a water-soluble polymer; a water-soluble organic solvent; a pH adjuster selected from the group consisting of an organic amine and its salt, and an organic acid and its salt; and a polyhydric alcohol, the chemical solution has better ability to remove defects on a patterned substrate including a substrate and a pattern containing magnetic particles. On the other hand, the comparative example did not exhibit the desired effect.
• Magnetic particles 39.23 parts by weight Dispersant (resin B2 above) 7.06 parts by weight Alkali-soluble resin 1 (resin D below) 13.60 parts by weight Photosensitive component (compound E below) 4.77 parts by weight Crosslinking agent (compound F below) 3.68 parts by weight Surfactant (KF-6001 (silicon-based surfactant, manufactured by Shin-Etsu Chemical Co., Ltd.)) 0.04 parts by mass Solvent (PGMEA) 31.62 parts by mass
• Resin D Resin with the following structure (Novolac type resin.
• R represents a substituent selected from the group consisting of a hydrogen atom, an alkyl group, an alkylene group, and an aryl group.
• the weight average molecular weight is about 8,000.
• Photosensitive component E Compound having the following structure (naphthoquinone diazide-substituted benzophenone derivative.
• R represents a hydrogen atom or a substituent represented by the following formula (N). However, at least one of the four R represents a substituent represented by the following formula (N). In formula (N), * represents a bond position).
• Crosslinker F Compound with the following structure
• the magnetic particle-containing composition prepared above was applied onto a silicon wafer to form a coating film, which was then dried at 100° C. for 2 minutes.
• the coating film was exposed through a mask having a predetermined opening using a USHIO simple exposure device under the condition of 200 mJ/cm 2 .
• the coating film after the exposure treatment was subjected to a heat treatment for 2 minutes using a hot plate at 90°C. Thereafter, using a simple developing device (manufactured by Mikasa Co., Ltd.), shower development was carried out for 30 seconds at 23° C.
• the developing solution used was FHD-5 manufactured by Fuji Film Electronic Materials Co., Ltd.
• a rinsing treatment was carried out by spraying the chemical solution shown in Table 1 for 15 seconds at 23° C. using a spray rinse nozzle, and then a rinsing treatment was carried out by spraying ultrapure water for 15 seconds at 23° C. using a spray rinse nozzle, and finally a spin drying treatment was carried out. Thereafter, a heat treatment (post-bake) was carried out for 5 minutes using a hot plate at 120° C. to obtain a silicon wafer and a laminate having a predetermined positive pattern on the silicon wafer.
• the obtained patterns were subjected to a defect evaluation similar to that in [Pattern formation and evaluation (1)], and the defect evaluation results were similar to those in the examples and comparative examples in [Pattern formation and evaluation (1)].

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