WO2021075305A1 - Composition durcissable négative, film durci, stratifié, procédé de fabrication de film durci, et dispositif à semi-conducteur - Google Patents

Composition durcissable négative, film durci, stratifié, procédé de fabrication de film durci, et dispositif à semi-conducteur Download PDF

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Publication number
WO2021075305A1
WO2021075305A1 PCT/JP2020/037800 JP2020037800W WO2021075305A1 WO 2021075305 A1 WO2021075305 A1 WO 2021075305A1 JP 2020037800 W JP2020037800 W JP 2020037800W WO 2021075305 A1 WO2021075305 A1 WO 2021075305A1
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group
curable composition
cross
negative curable
cured film
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PCT/JP2020/037800
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English (en)
Japanese (ja)
Inventor
雄一郎 榎本
青島　俊栄
健太 山▲ざき▼
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富士フイルム株式会社
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Priority to JP2021552331A priority Critical patent/JP7319381B2/ja
Publication of WO2021075305A1 publication Critical patent/WO2021075305A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing 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
    • G03F7/20—Exposure; 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
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a negative curable composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.
  • Polyimide resin is applied to various applications because it has excellent heat resistance and insulating properties.
  • the above application is not particularly limited, and examples of a semiconductor device for mounting include use as a material for an insulating film and a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.
  • the polyimide resin is used in the form of a negative curable composition containing an alkali-soluble polyimide resin.
  • a negative curable composition can be applied to a substrate by, for example, coating, and then exposed, developed, heated, etc., if necessary, to form a cured resin on the substrate. it can. Since the negative curable composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the applied negative curable composition at the time of application. It can be said that it has excellent manufacturing adaptability. In addition to the high performance of polyimide and the like, from the viewpoint of excellent adaptability in manufacturing, industrial application development of a negative curable composition containing an alkali-soluble polyimide is expected more and more.
  • Patent Document 1 states that it contains an alkali-soluble polyimide (a), an unsaturated bond-containing compound (b), a heat-crosslinkable compound (c), and a photopolymerization initiator (d) having a specific structure.
  • a characteristic photosensitive resin composition is described.
  • a negative curable composition containing an alkali-soluble polyimide it is desired to provide a negative curable composition having excellent chemical resistance of the obtained cured product.
  • the present invention relates to a negative curable composition having excellent chemical resistance of the obtained cured film, a cured film obtained by curing the negative curable composition, a laminate containing the cured film, and a method for producing the cured film. , And a semiconductor device including the cured film or the laminate.
  • Examples of typical embodiments of the present invention are shown below.
  • the silane coupling agent has a covalent bond between the alkoxy group e-1 directly bonded to the silicon atom and a group different from the e-1 and at least one of the plurality of types of cross-linking agents.
  • a negative curable composition having a possible group e-2.
  • the above-mentioned plurality of types of cross-linking agents have a cross-linking agent having a radically polymerizable group in which the cross-linking reaction proceeds by the action of a radical as a cross-linking group, and an acid cross-linking property in which the cross-linking reaction proceeds by the action of an acid as a cross-linking group.
  • the negative curable composition according to ⁇ 1> which comprises a cross-linking agent having a group.
  • ⁇ 4> The negative curable composition according to any one of ⁇ 1> to ⁇ 3>, wherein the alkali-soluble polyimide has a silicon atom.
  • ⁇ 5> The negative curable composition according to any one of ⁇ 1> to ⁇ 4>, wherein the alkali-soluble polyimide has an ethylenically unsaturated bond.
  • ⁇ 6> The negative curable composition according to any one of ⁇ 1> to ⁇ 5>, wherein the alkali-soluble polyimide has a phenolic hydroxy group.
  • ⁇ 7> The negative curable composition according to any one of ⁇ 1> to ⁇ 6>, which comprises a compound having at least one structure selected from the group consisting of a sulfonamide structure and a thiourea structure.
  • ⁇ 8> The negative curable composition according to any one of ⁇ 1> to ⁇ 7>, which contains a radical generator having an oxime structure.
  • ⁇ 9> The negative curability according to any one of ⁇ 1> to ⁇ 8>, which comprises a compound having 3 to 6 ethylenically unsaturated bonds as at least one of the plurality of types of cross-linking agents. Composition.
  • ⁇ 10> The negative curable composition according to any one of ⁇ 1> to ⁇ 9>, which contains a neutralized salt-type thermoacid generator.
  • ⁇ 11> The negative curable composition according to any one of ⁇ 1> to ⁇ 10>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 12> A cured film obtained by curing the negative curable composition according to any one of ⁇ 1> to ⁇ 11>.
  • ⁇ 13> A laminate containing two or more layers of the cured film according to ⁇ 12> and containing a metal layer between any of the cured films.
  • ⁇ 14> A method for producing a cured film, which comprises a film forming step of applying the negative curable composition according to any one of ⁇ 1> to ⁇ 11> to a substrate to form a film.
  • the method for producing a cured film according to ⁇ 14> which comprises an exposure step of exposing the film and a developing step of developing the exposed film.
  • a semiconductor device comprising the cured film according to ⁇ 12> or the laminate according to ⁇ 13>.
  • a negative type curable composition having excellent chemical resistance of the obtained cured film, a cured film obtained by curing the negative type curable composition, a laminate containing the cured film, and the cured film.
  • a manufacturing method and a semiconductor device including the cured film or the laminate are provided.
  • the present invention is not limited to the specified embodiments.
  • the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
  • the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
  • the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also exposure using particle beams such as an electron beam and an ion beam. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
  • (meth) acrylate means both “acrylate” and “methacrylate”, or either
  • (meth) acrylic means both “acrylic” and “methacryl”, or
  • Either, and "(meth) acryloyl” means both “acryloyl” and “methacryloyl”, or either.
  • Me in the structural formula represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the total solid content means the total mass of all the components of the composition excluding the solvent.
  • the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
  • GPC measurement gel permeation chromatography
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
  • the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as “upper”.
  • the opposite direction is referred to as "down”.
  • the composition may contain, as each component contained in the composition, two or more kinds of compounds corresponding to the component.
  • the content of each component in the composition means the total content of all the compounds corresponding to the component.
  • the temperature is 23 ° C.
  • the atmospheric pressure is 101,325 Pa (1 atm)
  • the relative humidity is 50% RH.
  • the combination of preferred embodiments is a more preferred embodiment.
  • the negative curable composition of the present invention contains an alkali-soluble polyimide, a plurality of cross-linking agents having different cross-linking groups, and a silane coupling agent, and the above-mentioned silane coupling agent is an alkoxy group directly bonded to a silicon atom. It has e-1 and a group e-2 which is different from the above e-1 and can form a covalent bond with at least one of the above-mentioned plurality of types of cross-linking agents.
  • the silane coupling agent having the above e-1 and the above e-2 is also referred to as a "specific silane coupling agent".
  • a cured film obtained from a negative curable composition containing an alkali-soluble polyimide, a plurality of cross-linking agents having different cross-linking groups, and a specific silane coupling agent is resistant. It was found to be excellent in chemical properties.
  • a polar solvent such as dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP)
  • an alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, or the above polar solvent.
  • a cured film having excellent chemical resistance is provided in which the solubility in a chemical such as a mixed solution of the above alkaline aqueous solution is suppressed.
  • a composition containing a solvent is further applied on the cured film.
  • it is considered to be useful because the dissolution and dispersion of the cured film in a chemical such as a solvent are suppressed when the film formed on the cured film is subjected to solvent development.
  • the mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
  • the specific silane coupling agent has the above e-1 and the above e-2. Therefore, in the cured film of the negative curable composition, the reaction between the e-2 and the cross-linking agent causes the compound after cross-linking of the cross-linking agent to contain the siloxane structure derived from the e-1. Conceivable. That is, the crosslinked compound becomes a compound having a siloxane structure. It is presumed that the cured film contains a compound after cross-linking having such a siloxane structure, so that the chemical resistance of the film is excellent. Further, it is considered that the compound after the cross-linking has the siloxane structure, so that the mechanical properties (break elongation) and the adhesion of the cured film are easily excellent.
  • Patent Document 1 does not describe or suggest that the chemical resistance of the cured film is improved by using the specific silane coupling agent.
  • the components contained in the negative curable composition of the present invention will be described in detail.
  • the negative curable composition of the present invention contains an alkali-soluble polyimide.
  • the alkali-soluble polyimide means a polyimide that dissolves 0.1 g or more at 23 ° C. in 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and 0.5 g or more from the viewpoint of pattern forming property.
  • a polyimide that dissolves is preferable, and a polyimide that dissolves 1.0 g or more is more preferable.
  • the upper limit of the dissolution amount is not particularly limited, but is preferably 100 g or less.
  • the alkali-soluble polyimide is preferably a polyimide having a plurality of imide structures in the main chain from the viewpoint of breaking elongation and insulating property of the obtained cured film.
  • the "main chain” refers to the relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the “side chain” refers to other binding chains.
  • the alkali-soluble polyimide preferably has a fluorine atom.
  • the fluorine atom is, for example, R 115 in the structure represented by the formula (1-1) described later, R 132 in the repeating unit represented by the formula (2-1) described later, or the formula (2-1) described later. ) Is preferably included in R 131 in the repeating unit, R 115 in the structure represented by the formula (1-1) described later, and R in the repeating unit represented by the formula (2-1) described later. It is more preferable that it is contained as an alkyl fluoride group in 132 or R 131 in the repeating unit represented by the formula (2-1) described later.
  • the amount of fluorine atoms with respect to the total mass of the alkali-soluble polyimide is preferably 1 to 50 mol / g, and more preferably 5 to 30 mol / g.
  • the alkali-soluble polyimide preferably has a silicon atom.
  • the silicon atom is preferably contained in R 131 in the repeating unit represented by the formula (2-1) described later, and will be described later in R 131 in the repeating unit represented by the formula (2-1) described later. It is more preferably contained as an organically modified (poly) siloxane structure. Further, the silicon atom or the organically modified (poly) siloxane structure may be contained in the side chain of the alkali-soluble polyimide, but is preferably contained in the main chain of the alkali-soluble polyimide.
  • the amount of silicon atoms with respect to the total mass of the alkali-soluble polyimide is preferably 0.01 to 5 mol / g, more preferably 0.05 to 1 mol / g.
  • the alkali-soluble polyimide preferably has an ethylenically unsaturated bond.
  • the alkali-soluble polyimide may have an ethylenically unsaturated bond at the end of the main chain or at the side chain, but it is preferably provided at the side chain.
  • the ethylenically unsaturated bond preferably has radical polymerization property.
  • the ethylenically unsaturated bond is R 115 in the structure represented by the formula (1-1) described later, R 132 in the repeating unit represented by the formula (2-1) described later, or the formula (2-2-) described later.
  • R 131 in the repeating unit represented by 1) It is preferably contained in R 131 in the repeating unit represented by 1), and is preferably contained in the formula (1-) described later.
  • the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by the formula (2-1) described later, and in the repeating unit represented by the formula (2-1) described later. It is more preferable that R 131 is contained as a group having an ethylenically unsaturated bond.
  • Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted, which is directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group, and a (meth) group.
  • Examples thereof include an acryloyloxy group and a group represented by the following formula (III).
  • R200 represents a hydrogen atom or a methyl group, and a methyl group is preferable.
  • (Poly) oxyalkylene group having 2 to 30 carbon atoms the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12 and 1 ⁇ 6 is more preferable, and 1 to 3 are particularly preferable), or a group in which two or more of these are combined is represented.
  • the (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
  • R 201 is preferably a group represented by any of the following formulas (R1) to (R3), and more preferably a group represented by the formula (R1).
  • L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) oxyalkylene group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded
  • X Indicates an oxygen atom or a sulfur atom
  • * represents a binding site with another structure
  • ⁇ represents a binding site with an oxygen atom to which R 201 in the formula (III) is bonded.
  • a preferred embodiment of the alkylene group having 2 to 12 carbon atoms in L or the (poly) oxyalkylene group having 2 to 30 carbon atoms is the above-mentioned R 201 having 2 to 12 carbon atoms. This is the same as the preferred embodiment of the 12 alkylene group or the (poly) oxyalkylene group having 2 to 30 carbon atoms.
  • X is preferably an oxygen atom.
  • * is synonymous with * in formula (III), and the preferred embodiment is also the same.
  • the structure represented by the formula (R1) comprises, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group and a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). Obtained by reacting.
  • the structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
  • the structure represented by the formula (R3) is obtained by reacting, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate). can get.
  • * represents a binding site with another structure, and is preferably a binding site with the main chain of polyimide.
  • the amount of the ethylenically unsaturated bond with respect to the total mass of the alkali-soluble polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.
  • the alkali-soluble polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.
  • the crosslinkable group other than the ethylenically unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
  • the crosslinkable group other than the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by the formula (2-1) described later, for example.
  • the amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the alkali-soluble polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.
  • the acid value of the alkali-soluble polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more.
  • the acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.
  • the acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
  • an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable, from the viewpoint of achieving both storage stability and developability.
  • the pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is expressed by its negative common logarithm pKa.
  • pKa is a value calculated by ACD / ChemSketch (registered trademark) unless otherwise specified.
  • the values published in "Revised 5th Edition Chemistry Handbook Basics" edited by the Chemical Society of Japan may be referred to.
  • the alkali-soluble polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.
  • the alkali-soluble polyimide preferably has a phenolic hydroxy group.
  • the alkali-soluble polyimide may have a phenolic hydroxy group at the end of the main chain or at the side chain.
  • the phenolic hydroxy group is, for example, R 115 in the structure represented by the formula (1-1) described later, R 132 in the repeating unit represented by the formula (2-1) described later, or the formula (2) described later. It is preferably contained in R 131 in the repeating unit represented by -1).
  • the amount of the phenolic hydroxy group with respect to the total mass of the alkali-soluble polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.
  • the alkali-soluble polyimide preferably has a structure represented by the following formula (1-1), and preferably has a structure represented by the following formula (1-1) in the main chain.
  • R 115 represents a tetravalent organic group.
  • R 115 is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (1-2) or formula (1-3).
  • Divalent selected from the group consisting of -CH 2- , -O-, -S-, -S ( O) 2- , -C (CF 3 ) 2- , and -C (CH 3 ) 2- It is more preferable that it is a group of. * Each independently represents a binding site with another structure.
  • tetravalent organic group represented by R 115 in the formula (1-1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. .. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
  • the tetracarboxylic dianhydride is preferably a compound represented by the following formula (1-4).
  • R 115 represents a tetravalent organic group.
  • R 115 has the same meaning as R 115 in formula (1-1), preferable embodiments thereof are also the same.
  • tetracarboxylic dianhydride examples include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4 , 4'-diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Dichloride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxy
  • DAA-1 to DAA-5 tetracarboxylic dianhydrides
  • DAA-5 tetracarboxylic dianhydrides
  • the alkali-soluble polyimide preferably has a repeating unit represented by the following formula (2-1), and preferably has a repeating unit represented by the following formula (2-1) in the main chain.
  • R 131 represents a divalent organic group
  • R 132 represents a tetravalent organic group.
  • the divalent organic group represented by R 131 includes a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, an organically modified (poly) siloxane structure or. Examples of a group in which two or more of these are combined are a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 3 to 20 carbon atoms.
  • An aromatic hydrocarbon group of 6 to 20, an organically modified (poly) siloxane structure, or a group in which two or more of these are combined is preferable, and an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable.
  • the linear or branched aliphatic group, the cyclic aliphatic group, or the aromatic group may have a substituent, and the substituent includes an alkyl group, a hydroxy group, a thiol group, and the like. Examples thereof include a carboxy group, a group having the above-mentioned ethylenically unsaturated bond, and a crosslinkable group other than the above-mentioned ethylenically unsaturated bond.
  • the organically modified (poly) siloxane structure includes both an organically modified siloxane structure containing only one siloxane structure and an organically modified polysiloxane structure containing two or more siloxane structures.
  • a structure represented by the following formula (SI-1) is preferable.
  • RS independently represents a hydrogen atom or an organic group, at least one of RS represents an organic group, n represents an integer of 1 or more, and * represents an integer or more independently.
  • RS is preferably a hydrogen atom, an alkyl group or an aryl group, respectively, and more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. Alkyl groups or phenyl groups having 1 to 4 carbon atoms are more preferable, methyl groups or phenyl groups are particularly preferable, and methyl groups are most preferable. Also, represents at least one organic group among structured R S, it is preferable that at least one of the two structured R S binding to each of the plurality of Si in the formula (SI-1) is an organic group of formula ( it is more preferable that all of the SI-1) in structured R S is an organic group.
  • n represents an integer of 1 or more, preferably an integer of 1 to 11, more preferably an integer of 1 to 3, and even more preferably 1 or 2. It is particularly preferably 0.
  • R 131 contains an organically modified (poly) siloxane structure
  • R 131 has a structure represented by the following formula (SI-2).
  • RS independently represents a hydrogen atom or an organic group
  • at least one of RS represents an organic group
  • L 1 is a linear or branched aliphatic aliphatic group.
  • L 2 is -Si ( RS ) 2- , a linear or branched aliphatic group, or a cyclic fat.
  • R S and n have the same meanings as R S and n in the above formula (SI-1), a preferable embodiment thereof is also the same.
  • L 1 is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and carbon.
  • L 2 is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and carbon.
  • An aromatic hydrocarbon group having a number of 6 to 20 or a group in which two or more of these are combined is preferable, and a linear aliphatic group having 2 to 20 carbon atoms is more preferable.
  • L 2 is also preferably a group represented by * 1- Si ( RS ) 2- L 3- * 2.
  • RS is as described above, * 1 represents a binding site with an oxygen atom in the formula (Si-2), L 3 is synonymous with L 1 described above, and the preferred embodiment is also the same, * 2 Is synonymous with * in which L 2 in equation (SI-2) is bound.
  • R 131 in formula (2-1) is preferably derived from diamine.
  • diamine used in the production of the alkali-soluble polyimide include linear or branched aliphatic, cyclic aliphatic or aromatic diamines, and two * in the structure represented by the above formula (SI-2). In each case, a compound that binds to an amino group and the like can be mentioned. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
  • the diamine is a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an organic modification (poly).
  • a diamine having a siloxane structure or a group containing two or more of these is preferable, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable.
  • the linear or branched aliphatic group, the cyclic aliphatic group, or the aromatic group may have a substituent, and the substituent includes an alkyl group, a hydroxy group, a thiol group, and the like.
  • Examples thereof include a carboxy group, a group having the above-mentioned ethylenically unsaturated bond, and a crosslinkable group other than the above-mentioned ethylenically unsaturated bond.
  • the group having an ethylenically unsaturated bond is a group that reacts with the above functional group after producing polyimide or a precursor compound thereof using a diamine having a functional group such as a hydroxy group, a thiol group or a carboxy group (for example).
  • Isocyanato group, hydroxy group, epoxy group, etc. and a compound having an ethylenically unsaturated bond may be introduced by reacting with the above-mentioned polyimide or a precursor compound thereof.
  • aromatic groups include:
  • a structure in which at least one hydrogen atom bonded to the benzene ring is substituted with a hydroxy group or a thiol group is also preferably mentioned.
  • the hydrogen atoms bonded to the benzene ring in AR-1 to AR-3 one or two have been substituted with a hydroxy group or a thiol group, or two in AR-5 to AR-10.
  • the benzene rings a structure in which one of the hydrogen atoms bonded to one benzene ring and one of the hydrogen atoms bonded to the other benzene ring are substituted with a hydroxy group or a thiol group is preferable.
  • diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane or isophoronediamine; meta or paraphenylenediamine, 2,5-dihydroxy-p-phenylenediamine , 2,5-Dimercapto-p-phenylenediamine, diaminotoluene, 4,
  • diamines (DA-1) to (DA-18) shown below are also preferable.
  • a diamine having at least two alkylene glycol units in the main chain is also mentioned as a preferable example.
  • a diamine containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule is preferable, and a diamine containing no aromatic ring is preferable.
  • Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, and Jeffamine (registered trademark).
  • EDR-148 EDR-148, Jeffamine® EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2)) -Aminopropoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propane-2-amine, etc., but are limited to these. Not done.
  • x, y, and z are arithmetic mean values.
  • R 131 in the formula (2-1) is preferably represented by ⁇ Ar 0 ⁇ L 0 ⁇ Ar 0 ⁇ from the viewpoint of the flexibility of the obtained cured film.
  • Ar 0 is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and a phenylene group is preferable.
  • the preferred range of L 0 is synonymous with A above.
  • R 131 in the formula (2-1) is preferably a divalent organic group represented by the following formula (51) or the formula (61) from the viewpoint of i-ray transmittance.
  • a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.
  • R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a fluoromethyl group. It is a difluoromethyl group, a trifluoromethyl group, a phenolic hydroxy group, or a thiol group, and * independently represents a binding site with another structure.
  • the monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group, a phenolic hydroxy group and a thiol group.
  • R 58 and R 59 are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups, or trifluoromethyl groups, respectively.
  • Examples of the diamine compound giving the structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2. Examples thereof include'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. One of these may be used, or two or more thereof may be used in combination.
  • the alkali-soluble polyimide may have only one type of repeating unit represented by the formula (2-1), or may have two or more types.
  • 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units is the alkali which is the repeating unit represented by the formula (2-1).
  • Soluble polyimide is exemplified. As an upper limit, 100 mol% or less is practical.
  • the weight average molecular weight (Mw) of the alkali-soluble polyimide is preferably 2,000 to 500,000, more preferably 2,500 to 100,000, and even more preferably 3,000 to 50,000.
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 1,500 to 50,000, and even more preferably 2,000 to 25,000.
  • the degree of dispersion of the molecular weight of the alkali-soluble polyimide is preferably 1.5 to 3.5, more preferably 2 to 3.
  • the degree of molecular weight dispersion means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).
  • alkali-soluble polyimide examples include, but are not limited to, the alkali-soluble polyimide used in the examples.
  • the alkali-soluble polyimide can be obtained, for example, by the method described in Examples. Specifically, an alkali-soluble polyimide can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine to obtain a precursor compound, and then heating the compound. Further, an alkali-soluble polyimide can be obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then heating the precursor compound obtained by reacting with a diamine.
  • the precursor compound or polyimide has a functional group such as a hydroxy group, a thiol group, or a carboxy group, a group that reacts with the functional group (for example, an isocyanato group, a hydroxy group, or an epoxy group) with respect to the precursor compound or polyimide.
  • a group that reacts with the functional group for example, an isocyanato group, a hydroxy group, or an epoxy group
  • Etc. and a compound having an ethylenically unsaturated bond is reacted with the above-mentioned polyimide or a precursor compound thereof, and in the case of a precursor compound, this is cyclized by heating or the like to obtain a polyimide having an ethylenically unsaturated bond. Be done.
  • the imidization rate (also referred to as “ring closure rate”) of the alkali-soluble polyimide is preferably 70% or more, and more preferably 80% or more, from the viewpoint of breaking elongation of the obtained cured film, insulating property, and the like. It is preferably 90% or more, and more preferably 90% or more.
  • the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
  • the imidization rate is measured by, for example, the following method.
  • the infrared absorption spectrum of the alkali-soluble polyimide is measured to determine the peak intensity P1 near 1377 cm -1, which is the absorption peak derived from the imide structure.
  • the alkali-soluble polyimide is heat-treated at 350 ° C. for 1 hour, and then the infrared absorption spectrum is measured again to obtain a peak intensity P2 in the vicinity of 1377 cm -1.
  • the content of the alkali-soluble polyimide in the negative curable composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total solid content of the negative curable composition. It is more preferably 40% by mass or more, and even more preferably 50% by mass or more.
  • the content of the alkali-soluble polyimide in the negative curable composition of the present invention is preferably 99.5% by mass or less, preferably 99% by mass or less, based on the total solid content of the negative curable composition. It is more preferably 98% by mass or less, further preferably 97% by mass or less, and even more preferably 95% by mass or less.
  • the negative curable composition of the present invention may contain only one type of alkali-soluble polyimide, or may contain two or more types of alkali-soluble polyimide. When two or more kinds are included, the total amount is preferably in the above range.
  • the negative curable composition of the present invention contains a plurality of types of cross-linking agents having different cross-linking groups.
  • the above-mentioned alkali-soluble polyimide or the compound corresponding to the specific silane coupling agent described later shall not correspond to the above-mentioned cross-linking agent.
  • crosslinkable group in the above-mentioned cross-linking agent examples include a (meth) acryloxy group, a (meth) acrylamide group, a vinyl group, an allyl group, a vinylphenyl group and other groups containing an ethylenically unsaturated bond, an epoxy group, an oxetanyl group and the like cyclic groups.
  • examples thereof include an alkoxymethyl group such as an ether group and a methoxymethyl group, a methylol group, and a benzoxazolyl group.
  • the negative curable composition contains a plurality of types of cross-linking agents having different cross-linking groups, that is, the negative curable composition includes a cross-linking agent having a certain cross-linking group A and the cross-linking group A.
  • the negative curable composition includes a cross-linking agent having a different kind of cross-linking group B.
  • the different crosslinkable groups may mean that the crosslinkable groups have different structures, but they are selected from the group consisting of the above-mentioned group containing an ethylenically unsaturated bond, a cyclic ether group, an alkoxymethyl group, and a methylol group. A combination of one type and another type selected from the above group is preferable.
  • a cross-linking agent having a group containing the ethylenically unsaturated bond as a cross-linking group is referred to as a "ethylene unsaturated bond-containing cross-linking agent”
  • a cross-linking agent containing the above-mentioned cyclic ether group as a cross-linking group is referred to as a "cyclic ether group-containing cross-linking agent”.
  • the cross-linking agent having the alkoxymethyl group as the cross-linking group is "alkoxymethyl group-containing cross-linking agent”
  • the cross-linking agent having the methylol group as the cross-linking group is "methylol group-containing cross-linking agent”
  • the cross-linking group is described above.
  • a cross-linking agent having a benzoxazolyl group is also referred to as a "benzoxazolyl group-containing cross-linking agent”.
  • the negative curable composition of the present invention preferably contains an ethylenically unsaturated bond-containing crosslinker as at least one of the above-mentioned plurality of crosslinkers, and is ethylenically. It is more preferable to contain a compound having 3 to 15 unsaturated bonds, and further preferably to contain a compound having 3 to 6 ethylenically unsaturated bonds. From the viewpoint of developability, the cross-linking agent is particularly preferably a compound having two ethylenically unsaturated bonds.
  • the negative curable composition according to the present invention includes an ethylenically unsaturated bond-containing cross-linking agent, a cyclic ether group-containing cross-linking agent, an alkoxymethyl group-containing cross-linking agent, a methylol group-containing cross-linking agent, and a benzoxazoli. It is preferable to contain at least two kinds of cross-linking agents selected from the group consisting of cross-linking agents containing ru groups, and it is preferable to contain cross-linking agents containing ethylenically unsaturated bonds, cross-linking agents containing cyclic ether groups, cross-linking agents containing alkoxymethyl groups, and methylol.
  • cross-linking agents selected from the group consisting of group-containing cross-linking agents, and the ethylenically unsaturated bond-containing cross-linking agent, the cyclic ether group-containing cross-linking agent, the alkoxymethyl group-containing cross-linking agent, and It is more preferable to include at least one cross-linking agent selected from the group consisting of methylol group-containing cross-linking agents.
  • a cross-linking agent having a radically polymerizable group in which the cross-linking reaction proceeds by the action of a radical as a cross-linking group and the cross-linking reaction proceed by the action of an acid as a cross-linking group It is preferable to include a cross-linking agent having an acid cross-linking group.
  • the radical is supplied by, for example, a photoradical polymerization initiator described later or a thermal radical polymerization initiator.
  • the acid is supplied by, for example, a photoacid generator or a thermoacid generator, which will be described later.
  • Examples of the radically polymerizable group include the above-mentioned group having an ethylenically unsaturated bond, and examples of the acid crosslinkable group include the above-mentioned cyclic ether group, alkoxymethyl group, methylol group, benzoxazolyl group and the like. ..
  • the negative curable composition of the present invention preferably contains an ethylenically unsaturated bond-containing cross-linking agent.
  • the group containing an ethylenically unsaturated bond in the ethylenically unsaturated bond-containing cross-linking agent include a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
  • the (meth) acryloyl group is preferable as the group containing the ethylenically unsaturated bond, and the (meth) acryloyl group is more preferable from the viewpoint of reactivity.
  • the ethylenically unsaturated bond-containing cross-linking agent is preferably a compound having radical polymerization property.
  • the crosslinker containing an ethylenically unsaturated bond may be a compound having one or more ethylenically unsaturated bonds, but a compound having two or more ethylenically unsaturated bonds is more preferable.
  • the compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above ethylenically unsaturated bonds.
  • the negative curable composition of the present invention may contain a compound having three or more ethylenically unsaturated bonds as an ethylenically unsaturated bond-containing cross-linking agent. preferable.
  • the compound having 3 or more ethylenically unsaturated bonds a compound having 3 to 15 ethylenically unsaturated bonds is preferable, and a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and 3 to 6 compounds are more preferable.
  • the compound having is more preferable.
  • the compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bond, and more preferably a compound having 3 to 15 ethylenically unsaturated bonds.
  • a compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
  • the negative curable composition of the present invention comprises a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable to include.
  • the molecular weight of the ethylenically unsaturated bond-containing cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the ethylenically unsaturated bond-containing cross-linking agent is preferably 100 or more.
  • ethylenically unsaturated bond-containing cross-linking agent examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters of unsaturated carboxylic acids and polyhydric alcohol compounds Preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds.
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amines or thiols, and a halogeno group.
  • Substitution reactions of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
  • a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether or the like As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-0273557 can be referred to, and these contents are incorporated in the present specification.
  • ethylenically unsaturated bond-containing cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
  • examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
  • a compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993.
  • Urethane (meth) acrylates such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.
  • a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
  • ethylene has a fluorene ring and is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like.
  • Compounds having two or more groups having a sex unsaturated bond and cardo resins can also be used.
  • JP-A-2015-187211 can also be used as the ethylenically unsaturated bond-containing cross-linking agent, and these contents are incorporated in the present specification.
  • Examples of the ethylenically unsaturated bond-containing cross-linking agent include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku Co., Ltd., A-TMMT: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nihon Kayaku Co., Ltd.), Di Pentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are ethylene glycol residues or propylene.
  • SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
  • Sartmer which is a bifunctional methacrylate having four ethyleneoxy chains.
  • Examples of the ethylenically unsaturated bond-containing cross-linking agent are as described in JP-A-48-041708, JP-A-51-0371993, JP-A-02-032293, and JP-B-02-016765.
  • Urethane acrylates and urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Is.
  • an ethylenically unsaturated bond-containing cross-linking agent an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238.
  • a compound having the above can also be used.
  • the ethylenically unsaturated bond-containing cross-linking agent may be an ethylenically unsaturated bond-containing cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group.
  • the ethylenically unsaturated bond-containing cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is added to the unreacted hydroxy group of the aliphatic polyhydroxy compound.
  • An ethylenically unsaturated bond-containing cross-linking agent which has been reacted to have an acid group is more preferable.
  • the aliphatic polyhydroxy compound is penta.
  • the acid value of the ethylenically unsaturated bond-containing cross-linking agent having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
  • the acid value of the ethylenically unsaturated bond-containing cross-linking agent is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizability is good.
  • the acid value of the ethylenically unsaturated bond-containing cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. The acid value is measured according to the description of JIS K 0070: 1992.
  • a monofunctional ethylenically unsaturated bond-containing cross-linking agent is preferably used as the ethylenically unsaturated bond-containing cross-linking agent from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the cured film. it can.
  • the monofunctional ethylenically unsaturated bond-containing cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, and carbitol (meth).
  • the monofunctional ethylenically unsaturated bond-containing cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
  • the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the negative curable composition of the present invention.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
  • the ethylenically unsaturated bond-containing cross-linking agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably in the above range.
  • the negative curable composition of the present invention preferably contains at least one cross-linking agent selected from the group consisting of a methylol group-containing cross-linking agent and an alkoxymethyl group-containing cross-linking agent.
  • a methylol group-containing cross-linking agent for example, formaldehyde or formaldehyde and alcohol are reacted with an amino group-containing compound such as melamine, glycoluryl, urea, alkylene urea, and benzoguanamine, and the hydrogen atom of the amino group is described.
  • Examples thereof include compounds having a structure in which the above is substituted with a methylol group or an alkoxymethyl group.
  • the method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
  • the cross-linking agent using melamine is a melamine-based cross-linking agent
  • the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent
  • the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent.
  • a cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
  • the negative curable composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and the glycoluril-based cross-linking agent and the glycol-based cross-linking agent described later are preferably contained. It is more preferable to contain at least one compound selected from the group consisting of melamine-based cross-linking agents.
  • melamine-based cross-linking agent examples include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutyl melamine and the like.
  • urea-based cross-linking agent examples include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol uryl.
  • Glycoluryl-based cross-linking agent such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, Monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethyl
  • Ethyleneurea-based cross-linking agents such as ethyleneurea, monobutoxymethylated, or dibutoxymethylated ethyleneurea, Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethyl
  • benzoguanamine-based cross-linking agent examples include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
  • Tetramethoxymethylated benzoguanamine Tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxy Methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like can be mentioned.
  • methylol group-containing cross-linking agent or the alkoxymethyl group-containing cross-linking agent a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferable.
  • aromatic ring preferably a benzene ring
  • Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylphenyl hydroxymethylbenzoate.
  • methylol group-containing cross-linking agent or the alkoxymethyl group-containing cross-linking agent
  • suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, and DML-.
  • the content thereof is 0.1 to 0.1 to the total solid content of the negative curable composition of the present invention. It is preferably 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. .. Only one type of the methylol group-containing cross-linking agent or the alkoxymethyl group-containing cross-linking agent may be contained, or two or more types may be contained. When two or more kinds of a methylol group-containing cross-linking agent or an alkoxymethyl group-containing cross-linking agent are contained, the total thereof is preferably in the above range.
  • the negative curable composition of the present invention preferably contains a cyclic ether group-containing cross-linking agent.
  • a cyclic ether group-containing cross-linking agent a cross-linking agent having an epoxy group as a cyclic ether group (epoxide compound) or a cross-linking agent having an oxetanyl group as a cyclic ether group (oxetanyl compound) is preferable.
  • the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
  • the epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the negative-type curable composition.
  • the epoxy compound preferably contains a polyethylene oxide group.
  • the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
  • epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , Trimethylol propantriglycidyl ether and other alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl ether and other polyalkylene glycol type epoxy resins; polymethyl (glycidyloxypropyl) siloxane and other epoxy groups Examples include, but are not limited to, containing silicones.
  • Epicron® 850-S Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by DIC Co., Ltd.), Rica Resin (registered trademark) BEO-60E (Product name, Shin Nihon Rika Co., Ltd.), EP-4003S, EP-4000S (trade name, manufactured by ADEKA Co., Ltd.), Serokiside 2021P, 2081, 2000, 3000, EHPE3150, Epolide GT400, Servinus B0134, B0177 ( Product name, manufactured by Daicel Co., Ltd
  • oxetane compound compound having an oxetanyl group
  • the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, and the like.
  • examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like.
  • the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone. Alternatively, two or more types may be mixed.
  • the content thereof shall be 0.1 to 30% by mass with respect to the total solid content of the negative curable composition of the present invention. Is more preferable, 0.1 to 20% by mass is more preferable, 0.5 to 15% by mass is further preferable, and 1.0 to 10% by mass is particularly preferable. Only one type of the cyclic ether group-containing cross-linking agent may be contained, or two or more types may be contained. When two or more kinds of cyclic ether group-containing cross-linking agents are contained, the total is preferably in the above range.
  • the negative curable composition of the present invention may contain a benzoxazolyl group-containing cross-linking agent.
  • the benzoxazolyl group-containing cross-linking agent is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and heat shrinkage is further reduced to suppress warpage.
  • benzoxazolyl group-containing cross-linking agent examples include BA-type benzoxazine, B-m-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), and a benzoxazine adduct of a polyhydroxystyrene resin.
  • BA-type benzoxazine trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • B-m-type benzoxazine trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • benzoxazine adduct of a polyhydroxystyrene resin examples thereof include phenol novolac type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.
  • the negative curable composition of the present invention contains a benzoxazolyl group-containing cross-linking agent
  • the content thereof is 0.1 to 30% by mass based on the total solid content of the negative photosensitive composition of the present invention. It is preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. Only one type of benzoxazolyl group-containing cross-linking agent may be contained, or two or more types may be contained. When two or more kinds of benzoxazolyl group-containing cross-linking agents are contained, the total is preferably in the above range.
  • Specific silane coupling agent In the negative curable composition of the present invention, between an alkoxy group e-1 directly bonded to a silicon atom and a group different from the above e-1 and at least one of the plurality of types of cross-linking agents. Includes a silane coupling agent (specific silane coupling agent) having a group e-2 capable of covalently bonding to.
  • the specific silane coupling agent may have only one alkoxy group e-1 directly bonded to the silicon atom or may have two or more alkoxy groups, but the obtained cured film may have chemical resistance and elongation at break. From the viewpoint of the above, it is preferable to have two or more, more preferably two or three, and further preferably three.
  • the alkoxy group in e-1 an alkoxy group having 1 to 10 carbon atoms is preferable, an alkoxy group having 1 to 4 carbon atoms is more preferable, and a methoxy group or an ethoxy group is more preferable.
  • the specific silane coupling agent preferably contains a monoalkoxysilyl group, a dialkoxysilyl group, or a trialkoxysilyl group as the group containing the above e-1, and preferably contains a dialkoxysilyl group or a trialkoxysilyl group. Is more preferable, and it is further preferable to contain a trialkoxysilyl group.
  • the alkoxy group contained in the monoalkoxysilyl group, the dialkoxysilyl group, or the trialkoxysilyl group corresponds to the alkoxy group e-1.
  • the two hydrogen atoms contained in the monoalkoxysilyl group or one hydrogen atom contained in the dialkoxysilyl group may be independently substituted with a group having e-2, which will be described later. , May be substituted with other known substituents.
  • the specific silane coupling agent may have only one silicon atom or may have two or more silicon atoms, but it is preferable that the specific silane coupling agent has only one silicon atom.
  • the above-mentioned alkoxy group e-1 may be bonded to at least one silicon atom, and the above-mentioned alkoxy group e-1 may be bonded to all silicon atoms.
  • e-2 that can form a covalent bond with a cross-linking agent
  • e-2 is not particularly limited as long as it is a group capable of covalently forming a covalent bond with at least one of the above-mentioned plurality of types of cross-linking agents, but is included in at least one of the above-mentioned plurality of types of cross-linking agents. It is preferably a group that can form a covalent bond with the group. That is, it is preferable that the group forms a covalent bond with the crosslinkable group of the crosslinking agent.
  • Examples of e-2 include a group containing an ethylenically unsaturated bond, a cyclic ether group, an alkoxymethyl group, a carboxy group, an amino group, a hydroxy group, a mercapto group, an acid anhydride group, an isocyanate group, a blocked isocyanate group and the like.
  • a group containing an ethylenically unsaturated bond, a cyclic ether group, or a carboxy group is preferable.
  • Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, and the like, a (meth) acryloyl group is preferable, and a (meth) group is preferable from the viewpoint of reactivity. Acryloyl groups are more preferred.
  • the group containing an ethylenically unsaturated bond is, for example, a group capable of covalently forming a covalent bond with a group containing an ethylenically unsaturated bond contained in an ethylenically unsaturated bond-containing cross-linking agent.
  • the alkoxymethyl group, carboxy group, amino group, hydroxy group, mercapto group, acid anhydride group, isocyanate group, or blocked isocyanate group is, for example, the cyclic ether group in the cyclic ether group-containing compound and the alkoxymethyl group-containing. It is a group that can form a covalent bond with the alkoxymethyl group contained in the compound or the methylol group contained in the methylol group-containing compound.
  • the specific silane coupling agent may have 1 or more e-2, and may have 2 or more. e-2 may be directly bonded to the specific silane coupling agent or may be bonded via a linking group, but it is preferably bonded via a linking group.
  • the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom is preferable.
  • Examples of preferred embodiments of the negative curable composition of the present invention are shown in (1) to (3) below.
  • An ethylenically unsaturated bond-containing cross-linking agent is included as one of the above-mentioned plurality of kinds of cross-linking agents.
  • e-2 a specific silane coupling agent having a group containing an ethylenically unsaturated bond is contained.
  • a cyclic ether group-containing cross-linking agent and an alkoxymethyl group-containing cross-linking agent are contained as one of the above-mentioned plurality of types of cross-linking agents.
  • It contains at least one cross-linking agent selected from the group consisting of a cross-linking agent and a methylol group-containing cross-linking agent, and as e-2, contains a specific silane coupling agent having a group containing a cyclic ether group (3).
  • One of the above-mentioned plurality of types of cross-linking agents contains at least one cross-linking agent selected from the group consisting of a cyclic ether group-containing cross-linking agent, an alkoxymethyl group-containing cross-linking agent, and a methylol group-containing cross-linking agent, and , E-2 contains a specific silane coupling agent having a group containing a carboxy group.
  • the specific silane coupling agent of the present invention preferably has a structure represented by the following formula (S-1).
  • (S1) E 1 represents an alkoxy group
  • L S1 represents n + 1 valent linking group
  • E 2 can result in covalent bonds between at least one of the plurality of types of crosslinking agent represents a group
  • n represents an integer of 1 or more
  • R S1 represents a substituent
  • a is an integer of 1 or more
  • b represents an integer of 1 or more
  • c is an integer of 0 or more
  • a The sum of b and c is 4.
  • E 1 is a group corresponding to the above-mentioned e-1, preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and a methoxy group or an ethoxy group. Groups are more preferred.
  • a is preferably 1, 2 or 3, more preferably 2 or 3, and even more preferably 3.
  • E 2 is a group corresponding to the above-mentioned e-2, and is a group containing an ethylenically unsaturated bond, a cyclic ether group, an alkoxymethyl group, a methylol group, a carboxy group, an amino group, and a hydroxy group.
  • a group, a mercapto group, an acid anhydride group, an isocyanate group, and a blocked isocyanate group are preferable, and a group containing an ethylenically unsaturated bond, a cyclic ether group, or a carboxy group is more preferable.
  • n is preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.
  • the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom is preferable.
  • b is preferably 1 or 2, and more preferably 1.
  • R S1 represents a substituent
  • R S1 may be used without any particular limitation known substituents in the field of the silane coupling agent is preferably an alkyl group or an aromatic hydrocarbon group .
  • c is preferably 0, 1 or 2, and more preferably 0.
  • the molecular weight of the specific silane coupling agent is preferably 100 to 2,000, more preferably 150 to 1,000.
  • Specific silane coupling agents include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyl.
  • the content of the specific silane coupling agent is preferably 0.1 to 30% by mass, preferably 0.5 to 15% by mass, based on the total solid content of the negative curable composition of the present invention. More preferably, it is more preferably 0.5 to 5% by mass.
  • the negative curable composition of the present invention may contain only one specific silane coupling agent, or may contain two or more of them. When two or more kinds are contained, the total is preferably in the above range.
  • the negative curable composition of the present invention may further contain a silane coupling agent other than the specific silane coupling agent.
  • a silane coupling agent a group e-2 which has an alkoxy group e-1 directly bonded to a silicon atom and can form a covalent bond with at least one of the above-mentioned plurality of types of cross-linking agents. Examples include silane coupling agents that do not have.
  • silane coupling agents examples include silane coupling agents having a ring structure such as an imidazole structure and an alkoxysilyl group, and silane coupling agents having an alkylamide structure such as N-trimethylsilylacetamide and an alkoxysilyl group. ..
  • the content of the other silane coupling agent is 0.1 with respect to the total solid content of the negative curable composition of the present invention. It is preferably about 30% by mass, more preferably 0.5 to 15% by mass, and even more preferably 0.5 to 5% by mass.
  • the negative curable composition of the present invention may contain only one type of other silane coupling agent, or may contain two or more types of other silane coupling agents. When two or more kinds are contained, the total is preferably in the above range.
  • the negative curable composition of the present invention preferably contains a radical generator.
  • a radical generator a photoradical generator or a thermal radical generator is preferable, and a photoradical generator is more preferable.
  • a radical generator having an oxime structure is preferable, and a photoradical generator having an oxime structure is more preferable.
  • the photoradical generator is not particularly limited, and for example, a compound known as a photoradical polymerization initiator can be appropriately selected.
  • a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
  • the photoradical generator is at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol -1 ⁇ cm -1 with respect to light having a wavelength in the range of about 300 to 800 nm (preferably 330 to 500 nm). It is preferably contained.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • a known compound can be arbitrarily used.
  • halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like.
  • paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.
  • Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated in the present specification.
  • KayaCure DETX manufactured by Nippon Kayaku Co., Ltd.
  • Nippon Kayaku Co., Ltd. is also preferably used.
  • a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
  • IRGACURE 184 (IRGACURE is a registered trademark)
  • DAROCUR 1173 As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF), Omnirad 907, Omnirad 369, and Omnirad 379 (all manufactured by IGM Resin). ) Can be used.
  • the compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
  • acylphosphine oxide-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • commercially available products such as IRGACURE-819, IRGACURE-TPO (trade name: all manufactured by BASF), Omnirad 819 and Omnirad TPO (all manufactured by IGM Resins) can be used.
  • metallocene compound examples include IRGACURE-784 (manufactured by BASF).
  • the photoradical generator examples include a photoradical generator (oxime compound) having an oxime structure.
  • oxime compound By using the oxime compound, the exposure latitude can be improved more effectively.
  • the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
  • the compound described in JP-A-2001-233842 the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.
  • Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
  • an oxime compound (oxime-based photoradical generator) as the photoradical generator.
  • IRGACURE OXE 01, IRGACURE OXE 02 (above, manufactured by BASF), and ADEKA PUTMER N-1919 are also suitable.
  • TR-PBG-304 manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.
  • Adeka Arkuru's NCI-831 and Adeka Arkuru's NCI-930 can also be used.
  • DFI-091 manufactured by Daito Chemix Co., Ltd.
  • an oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.
  • Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.
  • the photoradical generator includes trihalomethyltriazine compound, benzyldimethylketal compound, ⁇ -hydroxyketone compound, ⁇ -aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, and triarylimidazole. Selected from the group consisting of dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.
  • More preferred photoradical generators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds and trihalo.
  • At least one compound selected from the group consisting of a methyltriazine compound, an ⁇ -aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, a metallocene compound or an oxime compound is further preferable, and the oxime compound is more preferable. Even more preferable.
  • the photoradical generator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-, such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone).
  • RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like.
  • R I01 is a group represented by formula (II), the same as R I00
  • the groups, R I02 to R I04, are independently alkyls having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogens, respectively.
  • R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
  • the content of the photoradical generator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the negative curable composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photoradical generator may be contained, or two or more types may be contained. When two or more kinds of photoradical generators are contained, the total is preferably in the above range.
  • the negative curable composition of the present invention may further contain a thermal radical generator.
  • a thermal radical generator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding a thermal radical generator, the radical polymerization reaction further proceeds during heating, so that the crosslink density may be further improved.
  • thermal radical generator examples include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
  • thermal radical generator When a thermal radical generator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the negative curable composition of the present invention. %, More preferably 5 to 15% by mass. Only one type of thermal radical generator may be contained, or two or more types may be contained. When two or more types of thermal radical generators are contained, the total is preferably in the above range.
  • the negative curable composition of the present invention preferably contains an acid generator.
  • an acid generator a thermoacid generator or a photoacid generator is preferable, and a thermoacid generator is more preferable.
  • the thermal acid generator has the effect of generating an acid by heating and accelerating the cross-linking reaction of the above-mentioned cyclic ether group-containing cross-linking agent, alkoxymethyl group-containing cross-linking agent, methylol group-containing cross-linking agent and the like. In addition, dehydration condensation of the alkoxy group (e-1) in the specific silane coupling agent may be promoted.
  • the thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the composition is applied to the substrate, and during final heating (cure: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
  • the thermal decomposition start temperature is obtained as the peak temperature of the exothermic peak, which is the lowest temperature when the thermoacid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule. Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).
  • the acid generated from the thermoacid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane.
  • aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid
  • alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid
  • haloalkyl sulfonic acid such as sulfonic acid is preferable.
  • thermoacid generator include those described in paragraph 0055 of JP2013-072935A.
  • thermoacid generator the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermoacid generator.
  • the negative curable composition of the present invention preferably contains a neutralized salt-type thermoacid generator.
  • the pot life of a negative curable composition refers to viscosity stability when the composition is stored in the state of the composition without forming a cured film.
  • a neutralized salt type thermoacid generator as the thermoacid generator, a negative type curable composition having excellent pot life can be obtained. This is because when a neutralized salt type thermoacid generator is used, for example, even if an acid is generated once during storage, a neutralized salt is formed again and the progress of cross-linking of the cross-linking agent during storage is suppressed. It is presumed that this is because it is done.
  • the neutralized salt type thermoacid generator may be any thermoacid generator having a neutralized salt structure, and is preferably a thermoacid generator having an organic salt structure.
  • the neutralized salt structure refers to a structure having an acid-derived anion structure and a base-derived cation structure.
  • the anion structure is not particularly limited, and for example, aryl sulfonic acid such as p-toluene sulfonic acid, benzene sulfonic acid, dodecyl benzene sulfonic acid, methane sulfonic acid, ethane sulfonic acid,
  • the structure is preferably derived from an alkyl sulfonic acid such as butane sulfonic acid, or a haloalkyl sulfonic acid such as trifluoromethane sulfonic acid, and more preferably a structure derived from aryl sulfonic acid or haloalkyl sulfonic acid.
  • the cation examples include a cation derived from an organic compound, a cation derived from a metal, and the like, and a cation derived from an organic compound is preferable, and a cation derived from an amine compound or a quaternary ammonium compound is more preferable.
  • the cation is preferably a cation represented by the following formula (C-1) or the following formula (C-2).
  • RC11 to RC13 independently represent a hydrogen atom or a monovalent substituent.
  • RC21 to RC24 each independently represent a monovalent substituent.
  • RC11 to RC13 each independently preferably represent a hydrocarbon group, and more preferably an alkyl group or an aromatic hydrocarbon group.
  • RC21 to RC24 each independently preferably represent a hydrocarbon group, and more preferably an alkyl group or an aromatic hydrocarbon group. Further, at least one of RC21 to RC24 preferably represents an aromatic hydrocarbon group.
  • the neutralized salt type thermal acid generator a commercially available product may be used, and examples of the commercially available product include the K-PURE (registered trademark) series. Among these, the K-PURE (registered trademark) TAG -2179, TAG-2172, TAG-2713, TAG-2678, TAG-2679 and the like.
  • thermoacid generator When a thermoacid generator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the negative curable composition. It is preferably 2 to 15% by mass, more preferably 2 to 15% by mass. Only one type of thermoacid generator may be contained, or two or more types may be contained. When two or more types of thermoacid generators are contained, the total is preferably in the above range.
  • the negative curable composition of the present invention may contain a photoacid generator.
  • the photoacid generator is not particularly limited as long as it generates an acid by exposure, but is an onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime. Examples thereof include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl sulfonate.
  • Examples of the quinone diazide compound include the compounds described in paragraphs 0061 to 0063 of International Publication No. 2017/217292.
  • Examples of the onium salt compound or the sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.
  • a commercially available product may be used as the photoacid generator.
  • Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-376, WPAG-370, WPAG-469, WPAG-638, and WPAG-699. (Manufactured by Kojunyaku Co., Ltd.) and the like.
  • the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the negative type curable. It is more preferably 2 to 15% by mass. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more photoacid generators are contained, the total is preferably in the above range.
  • the negative curable composition of the present invention preferably contains a solvent.
  • a solvent a known solvent can be arbitrarily used.
  • the solvent is preferably an organic solvent.
  • the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
  • esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone.
  • alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)
  • 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate
  • Etc. eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate
  • 2-alkyloxy-2-methylpropionate etc.
  • Methyl acid and ethyl 2-alkyloxy-2-methylpropionate eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
  • methyl pyruvate, ethyl pyruvate, pyruvin Suitable examples include propyl acid acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate and the like.
  • ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol.
  • Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
  • ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferable.
  • aromatic hydrocarbons for example, toluene, xylene, anisole, limonene and the like are preferable.
  • sulfoxides for example, dimethyl sulfoxide is preferable.
  • N-methyl-2-pyrrolidone N-ethyl-2-pyrrolidone
  • N, N-dimethylacetamide N, N-dimethylformamide and the like are preferable.
  • the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
  • the mixed solvent to be mixed is preferable.
  • the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
  • the content of the solvent is preferably such that the total solid content concentration of the negative curable composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferable that the amount is 10 to 70% by mass, and more preferably 40 to 70% by mass.
  • the solvent content may be adjusted according to the desired thickness of the coating film and the coating method.
  • Only one type of solvent may be contained, or two or more types may be contained. When two or more kinds of solvents are contained, the total is preferably in the above range.
  • the negative curable composition of the present invention comprises a compound having at least one structure selected from the group consisting of a sulfonamide structure and a thiourea structure. Further, it is preferable to include it.
  • the sulfonamide structure is a structure represented by the following formula (S-1).
  • R represents a hydrogen atom or an organic group
  • R may be bonded to another structure to form a ring structure
  • * may independently form a binding site with another structure.
  • the R is preferably the same group as R 2 in the following formula (S-2).
  • the compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but a compound having one sulfonamide structure is preferable.
  • the compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or a monovalent organic group, and two or more of R 1 , R 2 and R 3 are bonded to each other. It may form a ring structure. It is preferable that R 1 , R 2 and R 3 are independently monovalent organic groups.
  • R 1 , R 2 and R 3 include a hydrogen atom, or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, and a carboxy group.
  • examples thereof include a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
  • the alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
  • a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable.
  • examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
  • an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like.
  • As the alkoxysilyl group an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable.
  • Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
  • aryl group an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable.
  • the aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
  • heterocyclic group examples include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isooxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a piperidine ring.
  • R 1 is an aryl group and R 2 and R 3 are independently hydrogen atoms or alkyl groups are preferable.
  • Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanylamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1.
  • the thiourea structure is a structure represented by the following formula (T-1).
  • R 4 and R 5 each independently represent a hydrogen atom or a monovalent organic group, and R 4 and R 5 may be combined to form a ring structure, where R 4 is.
  • the ring structure may be formed by combining with other structures to which * is bonded, R 5 may be combined with other structures to which * is bonded to form a ring structure, and * may be independently and others. Represents the site of connection with the structure of.
  • R 4 and R 5 are independently hydrogen atoms.
  • R 4 and R 5 include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, and a carbonyl group.
  • examples thereof include an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
  • the alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
  • a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable.
  • examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
  • an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like.
  • As the alkoxysilyl group an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable.
  • Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
  • aryl group an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable.
  • the aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
  • heterocyclic group examples include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isooxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a piperidine ring.
  • the compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferable.
  • the compound having a thiourea structure is preferably a compound represented by the following formula (T-2).
  • R 4 to R 7 each independently represent a hydrogen atom or a monovalent organic group, and at least two of R 4 to R 7 are bonded to each other to form a ring structure. You may.
  • R 4 and R 5 have the same meanings as R 4 and R 5 in formula (T-1), a preferable embodiment thereof is also the same.
  • R 6 and R 7 are independently monovalent organic groups.
  • the preferred embodiment of the monovalent organic group in R 6 and R 7 is the same as the preferred embodiment of the monovalent organic group in R 4 and R 5 in the formula (T-1). ..
  • Examples of compounds having a thiourea structure include N-acetylthiourea, N-allyl thiourea, N-allyl-N'-(2-hydroxyethyl) thiourea, 1-adamantyl thiourea, N-benzoyl thiourea, N, N'-.
  • Diphenylthiourea 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1- (3- (trimethoxysilyl) propyl) -3-methylthiourea, trimethyl Examples thereof include thiourea, tetramethylthiourea, N, N-diphenylthiourea, ethylenethiourea (2-imidazolinthione), carbimazole, and 1,3-dimethyl-2-thiohydranthin.
  • the content of the compound having at least one structure selected from the group consisting of the sulfonamide structure and the thiourea structure is 0.05 to 10% by mass with respect to the total mass of the negative curable composition of the present invention. It is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass.
  • the negative curable composition of the present invention may contain only one compound having at least one structure selected from the group consisting of a sulfonamide structure and a thiourea structure, or may contain two or more compounds. When only one type is contained, the content of the compound is preferably within the above range, and when two or more types are contained, the total amount thereof is preferably within the above range.
  • the negative curable composition of the present invention preferably further contains a migration inhibitor.
  • a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the negative curable composition layer.
  • the migration inhibitor is not particularly limited, but heterocycles (pyrazole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
  • triazole-based compounds such as 1,2,4-triazole and benzotriazole
  • tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.
  • an ion trap agent that traps anions such as halogen ions can also be used.
  • Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656.
  • the compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used.
  • the migration inhibitor include the following compounds.
  • the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the negative curable composition. , 0.05 to 2.0% by mass, more preferably 0.1 to 1.0% by mass.
  • the migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably in the above range.
  • the negative curable composition of the present invention preferably contains a polymerization inhibitor.
  • polymerization inhibitor examples include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'.
  • -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, Bis (4-hydroxy-3,5-ter
  • the content of the polymerization inhibitor is 0.01 to 5% by mass with respect to the total solid content of the negative curable composition of the present invention. It is preferably 0.02 to 3% by mass, more preferably 0.05 to 2.5% by mass.
  • the polymerization inhibitor may be only one type or two or more types. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
  • the negative curable composition of the present invention is, if necessary, various additives such as a sensitizer such as N-phenyldiethanolamine, a chain transfer agent, and a surfactant, as long as the effects of the present invention can be obtained.
  • a sensitizer such as N-phenyldiethanolamine
  • a chain transfer agent such as N-phenyldiethanolamine
  • a surfactant such as N-phenyldiethanolamine
  • Higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be blended.
  • the total blending amount is preferably 3% by mass or less of the solid content of the negative curable composition.
  • the negative curable composition of the present invention may contain a sensitizer.
  • the sensitizer absorbs specific active radiation and becomes an electron-excited state.
  • the sensitizer in the electron-excited state comes into contact with the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur.
  • the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids or bases.
  • the sensitizer include sensitizers such as N-phenyldiethanolamine.
  • the content of the sensitizer is 0.01 to 20% by mass with respect to the total solid content of the negative curable composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass.
  • the sensitizer may be used alone or in combination of two or more.
  • the negative curable composition of the present invention may contain a chain transfer agent.
  • Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pp. 683-684.
  • As the chain transfer agent for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
  • a thiol compound can be preferably used.
  • the content of the chain transfer agent is 0.01 to 20 mass by mass with respect to 100 parts by mass of the total solid content of the negative curable composition of the present invention. Parts are preferable, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable.
  • the chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.
  • Each type of surfactant may be added to the negative curable composition of the present invention from the viewpoint of further improving the coatability.
  • the surfactant various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used.
  • the following surfactants are also preferable.
  • the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit
  • the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.
  • the surfactant the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
  • the content of the surfactant is 0.001 to 2.0 mass by mass with respect to the total solid content of the negative curable composition of the present invention. %, More preferably 0.005 to 1.0% by mass.
  • the surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total is preferably in the above range.
  • Higher fatty acid derivative In the negative curable composition of the present invention, in order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added, and the negative curable composition is cured in the process of drying after application. It may be unevenly distributed on the surface of the sex composition.
  • the content of the higher fatty acid derivative is 0.1 to 10% by mass based on the total solid content of the negative curable composition of the present invention. It is preferable to have.
  • the higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.
  • the water content of the negative curable composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties.
  • Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.
  • the metal content of the negative curable composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, still more preferably less than 0.5 mass ppm, from the viewpoint of insulating properties. ..
  • Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range.
  • a raw material having a low metal content is selected as the raw material constituting the negative curable composition of the present invention.
  • Filter filtration is performed on the raw materials constituting the negative curable composition of the present invention, the inside of the apparatus is lined with polytetrafluoroethylene or the like, and distillation is performed under conditions in which contamination is suppressed as much as possible. The method can be mentioned.
  • the negative curable composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and 200 mass ppm from the viewpoint of wiring corrosiveness. More preferably less than mass ppm.
  • those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
  • the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
  • ion exchange treatment and the like are preferably mentioned.
  • a conventionally known storage container can be used as the storage container for the negative curable composition of the present invention.
  • a multi-layer bottle composed of 6 types and 6 layers of resin and 6 types of resin are used for the purpose of suppressing impurities from being mixed into the raw materials and the negative curable composition. It is also preferable to use a bottle having a 7-layer structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
  • the negative curable composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer. In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.
  • the negative curable composition of the present invention can be prepared by mixing each of the above components.
  • the mixing method is not particularly limited, and a conventionally known method can be used.
  • the filter pore diameter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
  • the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the filter may be one that has been pre-cleaned with an organic solvent.
  • a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times.
  • circulation filtration When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
  • impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
  • adsorbent a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
  • the cured film of the present invention is obtained by curing the negative curable composition of the present invention.
  • the film thickness of the cured film of the present invention can be, for example, 0.5 ⁇ m or more, and can be 1 ⁇ m or more. Further, the upper limit value can be 100 ⁇ m or less, and can be 30 ⁇ m or less.
  • the cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. It is preferable that the laminate of the present invention contains two or more cured films and includes a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferable.
  • the first cured film and the second cured film are both cured films of the present invention.
  • both the first cured film and the second cured film are the negative type of the present invention.
  • a preferred embodiment is a film obtained by curing the curable composition.
  • the negative curable composition of the present invention used for forming the first cured film and the negative curable composition of the present invention used for forming the second cured film have the same composition. It may be a product or a composition having a different composition.
  • the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
  • Examples of applicable fields of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
  • Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above.
  • the cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially in microelectronics.
  • the method for producing a cured film of the present invention includes a film forming step of applying the negative curable composition of the present invention to a substrate to form a film.
  • the method for producing a cured film of the present invention preferably includes the film forming step, an exposure step of exposing the film, and a developing step of developing the exposed film.
  • the method for producing a cured film of the present invention more preferably includes a heating step of heating the film. Specifically, it is also preferable to include the following steps (a) to (d).
  • A Film forming step of applying a negative curable composition to a substrate to form a film (negative curable composition layer)
  • Exposure step of exposing the film after the film forming step
  • Development step of developing the exposed film
  • Heating step of heating the developed film
  • the resin layer cured by exposure can be further cured.
  • the above-mentioned thermal acid generator is decomposed, and the generated acid promotes the cross-linking of the thermal cross-linking agent, so that sufficient curability can be obtained.
  • the method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention.
  • the method for producing the laminated body of the present embodiment is the step (a), the steps (a) to (c), or (a) after forming the cured film according to the above-mentioned method for producing the cured film. )-(D).
  • a laminated body can be obtained.
  • the production method includes a film forming step (layer forming step) in which a negative curable composition is applied to a substrate to form a film (layered).
  • the type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, There are no particular restrictions on magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like.
  • a semiconductor-made base material is particularly preferable, and a silicon base material is more preferable.
  • these base materials may be provided with a layer such as an adhesion layer or an oxide layer on the surface thereof.
  • the shape of the base material is not particularly limited, and may be circular or rectangular.
  • the size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.
  • a plate-shaped base material (board) is used as the base material.
  • the resin layer or the metal layer serves as a base material.
  • Coating is preferable as a means for applying the negative curable composition to the substrate.
  • the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method.
  • the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the negative curable composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable.
  • a resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the base material.
  • a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular base material, a slit coating method or a spray coating method is used.
  • the method, the inkjet method and the like are preferable.
  • the spin coating method for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. Further, it is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate.
  • the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention.
  • a step of removing the excess film at the edge of the base material may be performed. Examples of such a process include edge bead conditioner (EBR), air knife and the like.
  • EBR edge bead conditioner
  • the production method of the present invention may include a step of forming the film (negative curable composition layer), followed by a film forming step (layer forming step), and then drying to remove the solvent.
  • the preferred drying temperature is 50 to 150 ° C., more preferably 70 ° C. to 130 ° C., still more preferably 90 ° C. to 110 ° C.
  • the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
  • the production method of the present invention may include an exposure step of exposing the film (negative curable composition layer).
  • the exposure amount is not particularly determined as long as the negative curable composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ. It is more preferable to irradiate with / cm 2.
  • the exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
  • the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h.
  • Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples thereof include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), and (6) electron beam.
  • exposure with a high-pressure mercury lamp is particularly preferable, and exposure with an i-line is particularly preferable. As a result, particularly high exposure sensitivity can be obtained.
  • the production method of the present invention may include a developing step of developing the exposed film (negative curable composition layer) (developing the film). By developing, the unexposed portion (non-exposed portion) is removed.
  • the developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection from a nozzle, spray spraying, immersion of a developing solution in a base material, and the like, and ejection from a nozzle is preferably used.
  • the developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, a process in which the developer is vibrated by ultrasonic waves, and a process in which they are combined. It can be adopted.
  • Development is performed using a developer.
  • the developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
  • the developer preferably has an organic solvent content of 10% by mass or less based on the total mass of the developer, more preferably 5% by mass or less, and 1% by mass or less. Is more preferable, and a developing solution containing no organic solvent is particularly preferable.
  • the developer may contain a known surfactant.
  • the developing solution in alkaline development is more preferably an aqueous solution having a pH of 10 to 15. Examples of the alkaline compound contained in the developing solution in alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicate. Examples include potassium silicate, ammonia or amine.
  • amines examples include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, and tetramethylammonium hydroxide.
  • TMAH tetraethylammonium hydroxide
  • tetrabutylammonium hydroxide and the like can be mentioned.
  • an alkaline compound containing no metal is preferable, and an ammonium compound is more preferable.
  • the content of TMAH is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3 to the total mass of the developing solution. Mass% is more preferred.
  • the alkaline compound may be only one kind or two or more kinds. When there are two or more alkaline compounds, the total is preferably in the above range.
  • the development time is preferably 10 seconds to 5 minutes.
  • the temperature of the developing solution at the time of development is not particularly specified, but is usually 20 to 40 ° C.
  • the rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with water.
  • the rinsing time is preferably 5 seconds to 1 minute.
  • the production method of the present invention preferably includes a step (heating step) of heating the developed film.
  • the heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step.
  • cross-linking of an unreacted cross-linking agent can proceed.
  • the heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable.
  • the upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.
  • the heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
  • a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
  • the temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C.
  • the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started.
  • the temperature of the film (layer) after drying for example, from the boiling point of the solvent contained in the negative curable composition.
  • the heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.
  • the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C. from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the specific resin between the layers are undergoing a cross-linking reaction at this temperature.
  • Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed.
  • the heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547.
  • the pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
  • the pretreatment may be performed in two or more steps.
  • the pretreatment step 1 may be performed in the range of 100 to 150 ° C.
  • the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
  • cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
  • the heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the specific resin.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
  • the heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, and a hot air oven.
  • the production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (negative curable composition layer).
  • metal layer existing metal types can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, alloys containing these metals and the like are exemplified, and copper is used. And aluminum are more preferred, and copper is even more preferred.
  • the method for forming the metal layer is not particularly limited, and an existing method can be applied.
  • the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used.
  • photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
  • the thickness of the metal layer is preferably 0.1 to 50 ⁇ m, more preferably 1 to 10 ⁇ m in the thickest portion.
  • the production method of the present invention preferably further includes a laminating step.
  • the laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step are performed again on the surface of the cured film (resin layer) or the metal layer. , A series of steps including performing in this order. However, the mode may be such that only the film forming step (a) is repeated. Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated negative curable composition layers all at once.
  • the (c) developing step may be followed by the (e) metal layer forming step, and even if the heating is performed each time (d), the steps of (d) are collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step, and the like as appropriate.
  • the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step.
  • An example of the surface activation treatment is plasma treatment.
  • the laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times. Further, each layer in the laminating step may be a layer having the same composition, shape, film thickness, etc., or may be a different layer.
  • a structure such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer is preferable, and the resin layer is preferably 3 layers or more and 7 layers or less, and more preferably 3 layers or more and 5 layers or less.
  • a cured film (resin layer) of the negative curable composition so as to cover the metal layer after the metal layer is provided.
  • Examples thereof include an embodiment in which the steps, (b) exposure steps, (c) development steps, and (e) metal layer forming steps are repeated in this order, and (d) heating steps are collectively provided at the end or in the middle.
  • the present invention also discloses a semiconductor device containing the cured film or laminate of the present invention.
  • Specific examples of the semiconductor device in which the negative curable composition of the present invention is used to form the interlayer insulating film for the rewiring layer are described in paragraphs 0213 to 0218 and FIG. It can be taken into consideration and these contents are incorporated in the present specification.
  • ⁇ Synthesis example 1> [Alkali-soluble polyimide A-1: oxydiphthalic acid dianhydride, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 2 -Synthesis using isocyanatoethyl methacrylate] 65.56 g (179 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane while removing water in a drying reactor equipped with a flat bottom joint equipped with a stirrer, condenser and internal thermometer.
  • ⁇ Synthesis example 2> [Alkali-soluble polyimide A-2: oxydiphthalic acid dianhydride, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 2-isocyanate Synthesis using natoethylmethacrylate]
  • A-1 the same molar amount of 2,2-bis (3-amino-4-hydroxyphenyl) propane is used instead of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
  • Alkali-soluble polyimide A-2 was synthesized by the same method as that of A-1 except for the above.
  • Alkali-soluble polyimide A-3 Synthesis using oxydiphthalic dianhydride, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 2-isocyanatoethyl methacrylate]
  • the amount of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane used was 69. without using 1,3-bis (3-aminopropyl) tetramethyldisiloxane.
  • Alkali-soluble polyimide A-3 was synthesized by the same method as in the synthesis of A-1, except that the amount was 22 g (189 mmol).
  • ⁇ Synthesis example 4> [Alkali-soluble polyimide A-4: oxydiphthalic dianhydride, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and 1,3-bis (3-aminopropyl) tetramethyldisiloxane. Synthesis using] In the synthesis of A-1, the alkali-soluble polyimide A-4 was synthesized by the same method as in the synthesis of A-1, except that 2-isocyanatoethyl methacrylate was not added.
  • ⁇ Synthesis example 5> [Alkali-soluble polyimide A-5: oxydiphthalic dianhydride, 2,5-dimercapto-p-phenylenediamine, 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 2-isocyanatoethyl methacrylate were used. Synthetic] In the synthesis of A-1, except that the same molar amount of 2,5-dimercapto-p-phenylenediamine was used instead of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, A- Alkali-soluble polyimide A-5 was synthesized by the same method as in the synthesis of 1.
  • Examples and Comparative Examples> the components shown in Tables 1 to 3 below were mixed to obtain each negative curable composition. Further, in each comparative example, the components shown in Table 3 below were mixed to obtain each comparative composition. Specifically, the content of the components shown in Tables 1 to 3 was the amount shown in "Mass parts" in Tables 1 to 3. Further, in each composition, the solvent content was adjusted so that the solid content concentration of the composition was the value shown in Tables 1 to 3. In the table, for example, the description of "E-1 / E-4" and "0.5 / 0.5" refers to 0.5 parts by mass of E-1 and 0.5 parts by mass of E-4. It means that it was used.
  • the description in the column of "metal concentration” in Tables 1 to 3 represents the metal content (mass ppm) with respect to the total mass of the composition.
  • the obtained negative curable composition and the comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 ⁇ m. Further, in Tables 1 to 3, the description of "-" indicates that the composition does not contain the corresponding component.
  • [Radical generator] -C-1 ADEKA NCI-930 (manufactured by ADEKA Corporation)
  • C-2 Omnirad 819 (manufactured by IGM Resins)
  • C-3 Irgacure 784 (manufactured by BASF)
  • E-1 KBM-5103 (manufactured by Shin-Etsu Silicone Co., Ltd.)
  • E-2 N- (3- (triethoxysilyl) propyl) phthalamic acid
  • E-3 KBE-403 (manufactured by Shin-Etsu Silicone Co., Ltd.)
  • E-4 IM-1000 (manufactured by JX Nippon Mining & Metals Co., Ltd.)
  • E-1 to E-3 are compounds corresponding to the specific silane coupling agent. Since E-4 does not have the group e-2, it is a compound that does not correspond to the specific silane coupling agent.
  • each negative curable composition or comparative composition is applied (coated) in layers on a silicon wafer by a spin coating method to form a curable resin composition. A layer was formed.
  • the negative curable composition was applied (coated) in layers on a silicon wafer by the slit coating method to form a composition layer.
  • the silicon wafer to which the obtained composition layer was applied was dried on a hot plate at 80 ° C. for 5 minutes, and the curability of the thickness shown in Tables 1 to 3 was obtained on the silicon wafer. A resin composition layer was formed.
  • the curable resin composition layer on the silicon wafer was entirely exposed to an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C). After exposure, it was heated at 100 ° C. for 5 minutes.
  • the curable resin composition layer (resin layer) after heating is heated at a heating rate of 10 ° C./min under a nitrogen atmosphere to the temperature of "cure temperature (° C.)" in Tables 1 to 3. After reaching, this temperature was maintained for the time listed in "Cure Time (min)" in Tables 1-3.
  • the cured resin layer was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the resin layer was peeled off from the silicon wafer to obtain a resin film 1.
  • the elongation at break of the resin film 1 was set to a crosshead speed of 300 mm / min, a sample width of 10 mm, and a sample length of 50 mm using a tensile tester (Tensilon) at 25 ° C. and 65% relative humidity (RH) in the longitudinal direction of the film.
  • the measurement was performed in accordance with JIS-K6251: 2017 in an environment.
  • the elongation at break in the longitudinal direction was measured 5 times, and the arithmetic average value was used as an index value.
  • the evaluation was performed according to the following evaluation criteria. The evaluation results are described in the column of "evaluation of elongation at break" in Tables 1 to 3. It can be said that the larger the index value is, the more excellent the obtained cured film is in elongation at break.
  • C The above index value was 40% or less.
  • each of the prepared curable resin compositions or comparative compositions was applied onto a silicon wafer by a spin coating method to form a composition layer.
  • the negative curable composition was applied (coated) in layers on a silicon wafer by the slit coating method to form a composition layer.
  • the silicon wafer to which the obtained composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a composition layer having a uniform thickness of 15 ⁇ m on the silicon wafer.
  • composition layer on the silicon wafer was exposed to an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed composition layer (resin layer) was exposed at 10 ° C./ After the temperature is raised at a heating rate of 1 minute and reaches the temperature of "cure temperature (° C.)" in Tables 1 to 3, this temperature is set to the time shown in "cure time (min)” in Tables 1 to 3. It was maintained for a while to obtain a cured film. The obtained cured film was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
  • the dissolution rate was less than 200 nm / min.
  • B The dissolution rate was 200 nm / min or more and less than 300 nm / min.
  • C The dissolution rate was 300 nm / min or more.
  • each negative curable composition or comparative composition is applied (coated) in layers on a copper substrate by a spin coating method to form a curable resin composition. A layer was formed.
  • the negative curable composition was applied (coated) in layers on a copper substrate by the slit coating method to form a composition layer.
  • the copper substrate to which the obtained composition layer was applied was dried on a hot plate at 80 ° C. for 5 minutes, and the curability of the thickness shown in Tables 1 to 3 was obtained on the copper substrate. A resin composition layer was formed.
  • the curable resin composition layer on the copper substrate is exposed using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ / cm 2 using a photomask having a 100 ⁇ m square unmasked portion. After the exposure, the mixture was heated at 100 ° C. for 5 minutes. After the above heating, the mixture was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 5 minutes and rinsed with pure water for 20 seconds to obtain a 100 ⁇ m square resin layer.
  • the temperature is raised at a heating rate of 10 ° C./min, and after reaching the temperature of "cure temperature (° C.)" in Tables 1 to 3, the “cure time (cure time) in Tables 1 to 3 is reached. It was maintained for the time described in "min)".
  • the shear force of a 100 ⁇ m rectangular resin layer on a copper substrate was measured using a bond tester (CondorSigma, manufactured by XYZTEC) in an environment of 25 ° C. and 65% relative humidity (RH). It can be said that the larger the shearing force, the larger the adhesion force and the better the adhesion.
  • the evaluation was performed according to the following evaluation criteria. The evaluation results are described in the "Adhesion evaluation" column of Tables 1 to 3. -Evaluation criteria- A: The shearing force exceeded 40 gf. B: The shearing force was more than 25 gf and 40 gf or less. C: The shearing force was 25 gf or less. However, 1 gf is 9.80665 ⁇ 10 -3 N (Newton).
  • the negative curable composition containing the alkali-soluble polyimide, a plurality of types of cross-linking agents having different cross-linking groups, and a specific silane coupling agent according to the present invention has excellent chemical resistance. It can be seen that a cured film can be obtained.
  • the comparative composition according to Comparative Example 1 does not contain a specific silane coupling agent. It can be seen that the comparative composition according to Comparative Example 1 is inferior in chemical resistance in the obtained cured film.
  • Example 101 The negative curable composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin base material having the copper thin layer formed on the surface by a spin coating method, and dried at 80 ° C. for 5 minutes. After forming a negative curable composition layer having a film thickness of 20 ⁇ m, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). The exposure was performed through a mask (a binary mask having a pattern of 1: 1 line and space and a line width of 10 ⁇ m) at a wavelength of 365 nm. After exposure, it was heated at 100 ° C. for 5 minutes.
  • the mixture was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 5 minutes and rinsed with pure water for 20 seconds to obtain a layer pattern.
  • the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 200 ° C., the temperature was maintained at 200 ° C. for 120 minutes to form an interlayer insulating film for the rewiring layer.
  • the interlayer insulating film for the rewiring layer was excellent in insulating property.
  • a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

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Abstract

L'invention concerne : une composition durcissable négative permettant de produire un film durci présentant une excellente résistance chimique ; un film durci obtenu par durcissement de la composition durcissable négative ; un stratifié comprenant ledit film durci ; un procédé de fabrication dudit film durci ; et un dispositif à semi-conducteur comprenant ledit film durci ou ledit stratifié.　La composition durcissable négative selon l'invention contient un polyimide soluble dans un alcali, de multiples types d'agents de réticulation ayant différents groupes de réticulation, et un agent de couplage au silane, l'agent de couplage au silane ayant : un groupe alcoxy e-1 directement lié à un atome de silicium ; et un groupe e-2 qui est différent de e-1 et qui peut former une liaison covalente avec au moins l'un parmi les multiples types d'agents de réticulation. Le film durci est obtenu par durcissement de la composition durcissable négative. Le stratifié comprend le film durci. Le dispositif à semi-conducteur comprend le film durci ou le stratifié. Le procédé de production d'un film durci selon l'invention comprend une étape d'application de la composition durcissable négative sur un substrat pour former un film.
PCT/JP2020/037800 2019-10-18 2020-10-06 Composition durcissable négative, film durci, stratifié, procédé de fabrication de film durci, et dispositif à semi-conducteur WO2021075305A1 (fr)

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JP2013200328A (ja) * 2012-03-23 2013-10-03 Toray Ind Inc 感光性樹脂組成物およびそれからなるフィルム積層体
WO2017170249A1 (fr) * 2016-03-28 2017-10-05 東レ株式会社 Composition de résine photosensible
WO2017169574A1 (fr) * 2016-03-30 2017-10-05 東レ株式会社 Composition adhésive photosensible, produit durci, feuille adhésive photosensible, et procédé de fabrication d'un substrat stratifié et substrat stratifié comportant un motif adhésif
JP2017194677A (ja) * 2016-04-14 2017-10-26 旭化成株式会社 感光性樹脂組成物、硬化レリーフパターンの製造方法及び半導体装置
WO2018047688A1 (fr) * 2016-09-09 2018-03-15 東レ株式会社 Composition de résine
JP2019085431A (ja) * 2017-11-01 2019-06-06 東レ株式会社 光重合性モノマー、それを用いた感光性樹脂組成物および感光性樹脂組成物の硬化膜

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007004345A1 (fr) * 2005-06-30 2007-01-11 Toray Industries, Inc. Composition de résine photosensible et amplificateur d’adhésion
JP2011118191A (ja) * 2009-12-04 2011-06-16 Toray Ind Inc 有機−無機複合導電性パターン形成用感光性ペーストおよび有機−無機複合導電性パターンの製造方法
JP2013200328A (ja) * 2012-03-23 2013-10-03 Toray Ind Inc 感光性樹脂組成物およびそれからなるフィルム積層体
WO2017170249A1 (fr) * 2016-03-28 2017-10-05 東レ株式会社 Composition de résine photosensible
WO2017169574A1 (fr) * 2016-03-30 2017-10-05 東レ株式会社 Composition adhésive photosensible, produit durci, feuille adhésive photosensible, et procédé de fabrication d'un substrat stratifié et substrat stratifié comportant un motif adhésif
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JP2019085431A (ja) * 2017-11-01 2019-06-06 東レ株式会社 光重合性モノマー、それを用いた感光性樹脂組成物および感光性樹脂組成物の硬化膜

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