WO2020246234A1 - Composition durcissable négative, film durci, produit en couches, procédé de production de film durci, et dispositif à semi-conducteur - Google Patents

Composition durcissable négative, film durci, produit en couches, procédé de production de film durci, et dispositif à semi-conducteur Download PDF

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WO2020246234A1
WO2020246234A1 PCT/JP2020/019841 JP2020019841W WO2020246234A1 WO 2020246234 A1 WO2020246234 A1 WO 2020246234A1 JP 2020019841 W JP2020019841 W JP 2020019841W WO 2020246234 A1 WO2020246234 A1 WO 2020246234A1
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group
curable composition
negative curable
compound
cured film
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PCT/JP2020/019841
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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 JP2021524742A priority Critical patent/JP7334247B2/ja
Publication of WO2020246234A1 publication Critical patent/WO2020246234A1/fr

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    • 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
    • G03F7/20—Exposure; Apparatus therefor

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 insulation 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 or 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 base material by, for example, coating, and then exposed, developed, heated, etc., if necessary, to form a cured resin on the base material. it can. Since the negative curable composition can be applied by a known coating method or the like, for example, the negative curable composition can be manufactured with a high degree of freedom in designing the shape, size, application position, etc. of the applied negative curable composition. It can be said that the above adaptability is excellent. 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 film strength of the obtained cured product.
  • the present invention relates to a negative curable composition having excellent film strength 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.
  • An object of the present invention is to provide a semiconductor device including the cured film or the laminate.
  • ⁇ 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 curability according to any one of ⁇ 1> to ⁇ 6>, further comprising at least one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure.
  • Composition. ⁇ 8> The negative curable composition according to any one of ⁇ 1> to ⁇ 7>, wherein the content of the solvent is 30% by mass or more based on the total mass of the composition.
  • ⁇ 9> The negative curable composition according to any one of ⁇ 1> to ⁇ 8>, wherein the photoradical generator is an oxime compound.
  • ⁇ 10> The negative type curability according to any one of ⁇ 1> to ⁇ 9>, wherein the acid cross-linking agent contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent.
  • Composition. ⁇ 11> The negative curable composition according to any one of ⁇ 1> to ⁇ 10>, further comprising a radical cross-linking agent.
  • ⁇ 12> The negative curable composition according to ⁇ 11>, wherein the radical cross-linking agent contains a compound having 3 to 6 ethylenically unsaturated bonds.
  • ⁇ 13> The negative curable composition according to any one of ⁇ 1> to ⁇ 12>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 14> A cured film obtained by curing the negative curable composition according to any one of ⁇ 1> to ⁇ 13>.
  • ⁇ 15> A laminate containing two or more layers of the cured film according to ⁇ 14> and containing a metal layer between any of the cured films.
  • 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 ⁇ 13> to a substrate to form a film.
  • ⁇ 17> The method for producing a cured film according to ⁇ 16>, which comprises an exposure step of exposing the film and a developing step of developing the film.
  • ⁇ 18> The method according to ⁇ 16> or ⁇ 17>, which comprises a heating step of heating the film at a temperature higher than the acid generation temperature of the thermal acid generator and lower than the boiling point of the solvent.
  • Method for manufacturing a cured film ⁇ 19> A semiconductor device comprising the cured film according to ⁇ 14> or the laminate according to ⁇ 15>.
  • a negative type curable composition having excellent film strength of the obtained cured film, a cured film obtained by curing the negative type curable composition, a laminate containing the cured film, and the production of the cured film.
  • the 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 using 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 electron beams and ion beams. 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 “methacrylic", or
  • (meth) acryloyl means both “acryloyl” and “methacrylic", 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 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. and the atmospheric pressure is 101,325 Pa (1 atm).
  • the combination of preferred embodiments is a more preferred embodiment.
  • the negative curable composition of the present invention comprises an alkali-soluble polyimide, a photoradical generator, a thermoacid generator, an acid crosslinker, and a solvent having a boiling point higher than the acid generation temperature of the thermoacid generator (hereinafter referred to as “)”. It also contains "specific solvent"), and the content of the solvent is 10% by mass or more with respect to the total mass of the composition.
  • the negative curable composition of the present invention preferably further contains at least one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, which will be described later.
  • the negative curable composition of the present invention preferably further contains a radical cross-linking agent described later.
  • the negative curable composition of the present invention is a composition in which a non-exposed portion is removed by development when it is subjected to development after exposure.
  • the negative curable composition of the present invention is excellent in the film strength of the obtained cured film.
  • the mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
  • the negative curable composition is used for the purpose of obtaining a cured film by heating or the like after applying it to a substrate or the like. Further, if necessary, patterning may be performed by exposure and development, for example, before heating. In such a negative curable composition, it is considered that an acid is generated from the thermal acid generator during the heating, and the cross-linking reaction of the acid cross-linking agent proceeds with the acid to form a strong cured film. Be done.
  • the negative curable composition of the present invention contains a specific solvent. In a negative curable composition containing a specific solvent, it is considered that the acid is generated in a state where the specific solvent remains during the heating.
  • the acid easily moves in the film formed by applying the composition to the base material, for example, it is suppressed that a locally uncrosslinked region of the acid crosslinking agent remains in the obtained cured film. It is thought that.
  • the density (crosslink density) of the crosslinked structure derived from the acid crosslinking agent finally reached in the cured film is higher than that in the case where the negative curable composition contains only a solvent other than the specific solvent. It is considered to be. As a result, it is considered that a cured film having excellent film strength can be obtained.
  • the negative curable composition of the present invention by improving the above-mentioned cross-linking density, the permeation path of a solvent or the like in the cured film is reduced, and a cured film having excellent solvent resistance can be easily obtained. Conceivable. Further, since the crosslink density is likely to be improved even at a position near the interface between the base material and the cured film in the cured film, the negative curable composition of the present invention is cured with excellent adhesion to the base material. It is considered that a film is easily obtained.
  • Patent Document 1 does not describe or suggest a negative curable composition containing a thermoacid generator and a solvent having a boiling point higher than the acid generation temperature of the thermoacid generator.
  • 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 dissolved 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 film strength 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 in R 115 in the structure represented by the formula (1-1) described later and in the repeating unit represented by the formula (2-1) described later. It is more preferable that R 132 or R 131 in the repeating unit represented by the formula (2-1) described later is contained as a group having an ethylenically unsaturated bond. Among these, 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 an optionally substituted vinyl group 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.
  • 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 alkylene group of 12 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).
  • 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, and 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. * Independently represent 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 Dihydride, 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.
  • An example is a group in which two or more of these are combined, such as 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 carbon number of 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 examples of the substituent include an alkyl group, a hydroxy group, and a thiol group. 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 represent 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 each 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-chain aliphatic, cyclic aliphatic or aromatic diamines, and two * in the structure represented by the above formula (SI-2). Examples thereof include compounds that bind to amino groups. 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 examples of the substituent include an alkyl group, a hydroxy group, and a thiol group.
  • 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 are 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 Jeffamine (registered trademark) 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 ⁇ .
  • 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).
  • 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, a fluoromethyl group, It is a difluoromethyl group, a trifluoromethyl group, a phenolic hydroxy group, or a thiol group, and * represents a binding site with another structure independently.
  • Examples of the monovalent organic group of R 50 to R 57 include 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 (1-2), or may have two or more types.
  • 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all repeating units is an alkali which is a repeating unit represented by the formula (1-2).
  • 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 with respect to the precursor compound or polyimide (for example, an isocyanato group, a hydroxy group, or an epoxy group).
  • a group that reacts with the functional group with respect to the precursor compound or polyimide 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 film strength, insulating property, etc. of the obtained cured film. 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. Further, 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. 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 photoradical generator.
  • 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 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 may contain at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol -1 ⁇ cm -1 within the range of about 300 to 800 nm (preferably 330 to 500 nm). preferable.
  • 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).
  • any known compound can be used as the photoradical generator.
  • 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.
  • ketone compound for example, the compound described in paragraph 0087 of JP2015-087611A is exemplified, and the content thereof is 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 initiators 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 maximum absorption 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 is more preferably an 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, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052).
  • the radical polymerization initiator 2) is also preferably used.
  • 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 Corp.
  • 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 generators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triarylimidazoles. 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).
  • R I00 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 It is a group, and R I02 to R I04 are independently alkyl having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, or halogen.
  • 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 contains a thermoacid generator.
  • the thermoacid generator is not particularly limited as long as it is a compound that generates an acid by heat, but for example, an onium salt such as a sulfonium salt, an ammonium salt, or a phosphonium salt, a carboxylic acid ester compound, a sulfonic acid ester compound, or a phosphoric acid. Examples thereof include ester compounds such as ester compounds.
  • thermoacid generator examples include sulfonic acid, phosphoric acid, and carboxylic acid, with sulfonic acid being preferable and aromatic sulfonic acid being more preferable.
  • the pKa of the acid generated from the thermoacid generator is preferably -15 to 3, more preferably -10 to 0.
  • the acid generation temperature of the thermoacid generator is preferably 40 to 300 ° C., more preferably 80 to 260 ° C., further preferably 120 to 220 ° C., and 120 ° C. to 200 ° C. Is particularly preferable, and the temperature is most preferably 140 ° C to 180 ° C.
  • the acid generation temperature is determined 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 acid generation temperature include Q2000 (manufactured by TA Instruments).
  • thermoacid generators examples include Sun Aid SI series manufactured by Sanshin Kagaku Kogyo, CPI series manufactured by Sun Appro, and K-PURE TAG series manufactured by King. Further, Japanese Patent Application Laid-Open No. 2003-277353, Japanese Patent Application Laid-Open No. 2-001470, Japanese Patent Application Laid-Open No. 2-255646, Japanese Patent Application Laid-Open No. 3-01044, Japanese Patent Application Laid-Open No. 2003-183313, Japanese Patent Application Laid-Open No. 2003-277352, Japanese Patent Application Laid-Open No. 58-037003 No., known thermoacid generators described in JP-A-58-198532 and the like can also be used.
  • the content of the thermoacid 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. , 0.5 to 15% by mass is more preferable, and 1.0 to 10% by mass is particularly preferable. 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 contains an acid cross-linking agent.
  • the acid cross-linking agent is particularly limited as long as it is a compound having a plurality of groups in the molecule in which a reaction forming a covalent bond with another compound in the composition or a reaction product thereof is promoted by the action of an acid.
  • a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to a nitrogen atom.
  • Compounds having a structure are more preferable.
  • an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is replaced with a methylol group or an alkoxymethyl group.
  • an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine
  • formaldehyde or formaldehyde and alcohol examples thereof include compounds having the above-mentioned structure.
  • 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.
  • an acid cross-linking agent using melamine is a melamine-based cross-linking agent
  • an acid cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent
  • an acid cross-linking agent using alkylene urea is an alkylene.
  • Those using a urea-based cross-linking agent and benzoguanamine are called benzoguanamine-based cross-linking agents.
  • 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 described later and 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.
  • Glycol-uryl cross-linking agent Urea-based cross-linking agents 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 chloride, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea, Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene ure
  • benzoguanamine-based cross-linking agent examples include monohydroxymethylated benzoguanamine and dihydroxymethylated benzoguanamine. Trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated Benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, Examples thereof include tetrabutoxymethylated benzogu
  • a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
  • a compound to which a group is directly bonded is also preferably used.
  • Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylphenyl hydroxymethylbenzoate.
  • suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP- Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML- BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM
  • the negative curable composition of the present invention preferably contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as an acid cross-linking agent.
  • Epoxy compound compound having an epoxy group
  • 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 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.
  • an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance.
  • an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance.
  • Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain polyethylene oxide groups.
  • oxetane compound compound having an oxetanyl group
  • examples of 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.
  • Benzoxazine compound (compound having a benzoxazolyl group) Since the benzoxazine compound is a cross-linking reaction derived from the ring-opening addition reaction, degassing does not occur during curing, and the heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.
  • benzoxazine compound Preferred examples of the benzoxazine compound are BA type benzoxazine, Bm type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzo.
  • Oxazine compounds can be mentioned. These may be used alone or in combination of two or more.
  • the content of the acid cross-linking agent 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 particularly preferably 1.0 to 10% by mass. Only one type of acid cross-linking agent may be contained, or two or more types may be contained. When two or more kinds of acid cross-linking agents are contained, the total is preferably in the above range.
  • the negative curable composition of the present invention contains a specific solvent.
  • the specific solvent is a solvent having a boiling point higher than the acid generation temperature of the thermal acid generator.
  • a solvent having a boiling point higher than the lowest acid generation temperature among the acid generation temperatures of the plurality of thermoacid generators may be used, and the acid generation temperature is the highest. It is preferably a solvent having a boiling point higher than that of the above.
  • the specific solvent is preferably a solvent having a boiling point higher than the heating temperature in the film heating step described later.
  • the boiling point of the specific solvent is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, further preferably 30 ° C.
  • the upper limit of the boiling point is not particularly limited, but it is preferably a temperature of (acid generation temperature of the thermal acid generator + 100 ° C.) or less.
  • the boiling point of the specific solvent is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, more preferably 160 ° C. or higher, further preferably 180 ° C. or higher, and further preferably 200 ° C. or higher. Is particularly preferred.
  • the boiling point is preferably 300 ° C. or lower, more preferably 280 ° C. or lower, and even more preferably 250 ° C. or lower.
  • the boiling point of the specific solvent can be measured as the temperature at which the specific solvent boils in air at 1 atm.
  • the specific solvent is preferably a solvent having a heterocyclic structure.
  • the solvent having a heterocyclic structure include a solvent having a lactone structure such as ⁇ -butyrolactone, ⁇ -caprolactone and ⁇ -valerolactone, and a lactam structure such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.
  • examples thereof include a solvent and a solvent having a cyclic ether structure such as tetrahydrofuran.
  • a solvent having a lactone structure is preferable, ⁇ -butyrolactone or ⁇ -caprolactone is more preferable, and ⁇ -butyrolactone is further preferable.
  • the negative curable composition of the present invention preferably further contains another solvent as the specific solvent in addition to the solvent having a heterocyclic structure.
  • the other solvent is not particularly limited, and examples thereof include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
  • esters for example, ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyloxyoxyacetate alkyl (eg,) Methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionate alkyl esters (eg For example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc.
  • ethers include diethylene glycol dimethyl ether, 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 monomethyl ether.
  • Suitable examples include 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, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropanamide and the like are preferable.
  • the negative curable composition of the present invention preferably contains the above-mentioned solvent having a heterocyclic structure and another solvent.
  • One selected solvent or a mixed solvent composed of two or more is preferable.
  • At least one solvent selected from the group consisting of ⁇ -butyrolactone, ⁇ -caprolactone, and N-methyl-2-pyrrolidone and at least one selected from the group consisting of dimethyl sulfoxide and ethyl lactate. It is preferable to use one kind of solvent in combination, and at least one solvent selected from the group consisting of ⁇ -butyrolactone and ⁇ -caprolactone, and at least one selected from the group consisting of dimethyl sulfoxide and ethyl lactate. It is more preferable to use one kind of solvent in combination, and it is further preferable to use ⁇ -butyrolactone and dimethyl sulfoxide in combination.
  • the content of the specific solvent is 10% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass or more with respect to the total mass of the composition.
  • the upper limit of the content is not particularly limited, but is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less.
  • the negative curable composition of the present invention preferably contains 10% by mass or more of the solvent having the above-mentioned heterocyclic structure with respect to the total mass of the composition.
  • the content is more preferably 20% by mass or more, and further preferably 30% by mass or more.
  • the upper limit of the content is not particularly limited, but is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less.
  • the content of the solvent having the above-mentioned heterocyclic structure with respect to the total mass of the specific solvent is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. It is particularly preferably 60% by mass or more.
  • the content may be 100% or less, preferably 95% or less, and more preferably 90% or less. Only one type of the specific 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 may contain a solvent other than the specific solvent.
  • the solvent other than the specific solvent include a solvent having a boiling point lower than the acid generation temperature of the thermal acid generator.
  • the negative curable composition contains a thermoacid generator having an acid generation temperature of 150 ° C.
  • ⁇ -butyrolactone (boiling point: 204 ° C.) and ethyl lactate (boiling point: 154 ° C.) are specific solvents.
  • thermoacid generator having an acid generation temperature of 180 ° C.
  • ⁇ -butyrolactone corresponds to a specific solvent
  • ethyl lactate does not correspond to a specific solvent.
  • thermoacid generator having an acid generation temperature of 220 ° C. neither ⁇ -butyrolactone nor ethyl lactate corresponds to the specific solvent.
  • the content of the solvent other than the specific solvent in the negative curable composition of the present invention is preferably 10 to 80% by mass, more preferably 10 to 60% by mass, based on the total mass of the composition. It is more preferably 10 to 50% by mass.
  • the negative curable composition of the present invention may be in a mode in which a solvent other than the specific solvent is substantially not contained.
  • the content of the solvent other than the specific solvent is preferably 5% by mass or less, more preferably 3% by mass or less, and 1% by mass with respect to the total mass of the composition. It is more preferably% or less, and particularly preferably 0.1% by mass or less. Further, the content can be set to 0% by mass.
  • the negative curable composition of the present invention does not substantially contain a solvent other than the specific solvent, it is preferable to use a solvent having a heterocyclic structure and the other solvent described above in combination as the specific solvent. Further, the total content of the specific solvent and the solvent other than the specific solvent in the negative curable composition of the present invention (if the solvent other than the specific solvent is not contained, the content of the specific solvent) is determined from the viewpoint of coatability.
  • the total solid content concentration of the negative curable composition of the present invention is preferably 5 to 80% by mass, more preferably 5 to 75% by mass, and 10 to 70% by mass. It is more preferable that the amount is 40 to 70% by mass.
  • the above content may be adjusted according to a desired thickness and coating method.
  • the negative curable composition of the present invention preferably further contains a radical cross-linking agent.
  • the radical cross-linking agent is a compound having a radically polymerizable group.
  • a group containing an ethylenically unsaturated bond is preferable.
  • the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as 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 radical cross-linking agent 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 preferably contains a compound having three or more ethylenically unsaturated bonds as a radical cross-linking agent.
  • 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 three or more ethylenically unsaturated bonds is preferably a compound having three 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 radical 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 radical cross-linking agent is preferably 100 or more.
  • radical 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, and are preferable.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group.
  • 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.
  • radical cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
  • examples include polyethylene glycol di (meth) acrylate, trimethylol ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and 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.
  • radical cross-linking agent other than the above, it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like.
  • Compounds having two or more radicals and cardo resins can also be used.
  • the compound described in Japanese Patent Application Laid-Open No. 10-062986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol is also (meth) acrylated. It can be used as a radical cross-linking agent.
  • dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol 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 mediated by ethylene glycol residues or propylene glycol residues. A structure that is bonded together is preferable
  • SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
  • SR-209 which is a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartmer. 231 and 239
  • DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd.
  • TPA-330 a trifunctional acrylate having 3 isobutyleneoxy chains
  • urethane oligomer UAS-10 examples include, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and SR-209, which is a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartmer. 231 and 239, DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 iso
  • UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Japan) Chemicals Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.
  • radical cross-linking agent examples include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765.
  • 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.
  • radical cross-linking agent a compound having 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 is used. You can also do it.
  • the radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group.
  • the radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
  • a radical cross-linking agent provided with is more preferable.
  • the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound.
  • examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the preferable acid value of the radical cross-linking agent having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
  • the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizable property is good.
  • the acid value is measured according to the description of JIS K 0070: 1992.
  • a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the cured film.
  • the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth).
  • 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.
  • One type of radical cross-linking agent may be used alone, or two or more types may be mixed and used. 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 is at least one selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure. It is preferable to further contain a compound of the species.
  • 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 to form a ring structure. May be formed. It is preferable that R 1 , R 2 and R 3 are independently monovalent organic groups.
  • R 1 , R 2 and R 3 include hydrogen atoms, or alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, arylether groups, carboxyl groups, 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 and a pentoxy group.
  • 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 hydrogen atoms, or alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, 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 and a pentoxy group.
  • 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 is preferably a compound having one thiourea structure.
  • the compound having a thiourea structure is preferably a compound represented by the following formula (T-2).
  • R 4 to R 7 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 total content of the compound having a sulfonamide structure and the compound having a thiourea structure is preferably 0.05 to 10% by mass, preferably 0.1 to 5% by mass, based on the total mass of the negative curable composition of the present invention. It is more preferably by mass%, and even more preferably 0.2 to 3% by mass.
  • the negative curable composition of the present invention may contain only one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having 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 preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
  • a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
  • the metal adhesiveness improving agent include a silane coupling agent.
  • silane coupling agent examples include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992.
  • Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Further, it is also preferable to use the following compounds as the silane coupling agent.
  • Et represents an ethyl group.
  • the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used. ..
  • the content of the metal adhesive improving agent is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0 with respect to 100 parts by mass of the alkali-soluble polyimide. It is in the range of .5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are good.
  • the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.
  • the negative curable composition of the present invention can be subjected to various additives such as a thermoacid generator, a sensitizer such as N-phenyldiethanolamine, and chain transfer, if necessary, as long as the effects of the present invention can be obtained.
  • additives such as a thermoacid generator, a sensitizer such as N-phenyldiethanolamine, and chain transfer, if necessary, as long as the effects of the present invention can be obtained.
  • Agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, antiaggregating 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 a thermal radical generator, a photoradical generator, or the like, and causes actions such as electron transfer, energy transfer, and heat generation.
  • the thermal radical generator and the photoradical generator 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, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005).
  • As the chain transfer agent for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. These can generate radicals by donating hydrogen to low-activity radicals to generate radicals, or by deprotonating after being oxidized.
  • 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. Only one type of surfactant may be used, or two or more types may be used. 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.
  • 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, it is preferable that the total of these metals is 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.
  • 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 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 material of the filter 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 a plurality of types of filters are used, 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 a 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.
  • 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 may be patterned by etching. For these applications, for example, Science & Technology Co., Ltd.
  • 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 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 for exposing the film, and a developing step for developing the film. Further, it is more preferable that the method for producing a cured film of the present invention 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) (b) An exposure step of exposing the film after the film forming step (c) Development step of developing the exposed film (d) Heating step of heating the developed film By heating in the heating step, 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 acid 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) of applying a negative curable composition 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 transistor.
  • semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film transistor.
  • magnetic film 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.
  • 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 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 substrate.
  • a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable.
  • 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. 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 transfer method 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.
  • 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 drying step it is sufficient that at least a part of the solvent is removed, and it is preferable that not all of the solvent is removed.
  • 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 defined 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 performing the development, 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 for example, a developing method such as paddle, spray, immersion, or ultrasonic wave 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 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 hydrogencarbonate, potassium hydrogencarbonate, 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) or tetraethylammonium hydroxide and the like.
  • TMAH tetraethylammonium hydroxide
  • an alkaline compound containing no metal is preferable, and an ammonium compound is more preferable.
  • 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.
  • the heating step for example, the above-mentioned thermal acid generator is decomposed to generate an acid, and the cross-linking reaction of the acid cross-linking agent proceeds.
  • the alkali-soluble polyimide may have an ethylenically unsaturated bond
  • the negative curable composition of the present invention may contain a radical cross-linking agent, but is ethylenically in an unreacted alkali-soluble polyimide.
  • 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 temperature in the heating step is preferably a temperature higher than the acid generation temperature of the thermal acid generator and lower than the boiling point of the specific solvent.
  • 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. It is also preferable to gradually raise the temperature from a temperature as low as 30 to 200 ° C.
  • 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 alkali-soluble polyimide 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 carry out 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 with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the alkali-soluble polyimide.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
  • 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 and tungsten are exemplified, copper and aluminum are more preferable, and copper is preferable. 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.
  • the resin layer is 3 or more and 7 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and 3 or more and 5 or less are more preferable.
  • 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. 1 of JP-A-2016-027357. These contents can be taken into consideration and are incorporated herein by reference.
  • Examples and Comparative Examples> In each example, the components listed in Table 1 or Table 2 below were mixed to obtain each negative curable composition. Further, in each comparative example, the components shown in Table 2 below were mixed to obtain each comparative composition. Specifically, the content of the component shown in Table 1 or Table 2 was the amount shown in "Mass part" of Table 1 or Table 2. Further, in each composition, the solvent content was adjusted so that the solid content concentration of the composition was the value shown in Table 1 or Table 2. The description in the column of "metal concentration" in Table 1 or Table 2 represents the metal content (mass ppm) with respect to the total mass of the composition.
  • the obtained negative curable composition and comparative composition were pressure-filtered through a polytetrafluoroethylene filter having a pore width of 0.8 ⁇ m. Further, in Table 1 or Table 2, the description of "-" indicates that the composition does not contain the corresponding component.
  • E-1 isopropyl p-toluenesulfonic acid
  • E-2 K-PURE TAG-2179 (manufactured by King)
  • E-3 K-PURE TAG-2713 (manufactured by King)
  • E-4 K-PURE TAG-2690 (manufactured by King)
  • Example 19 [Evaluation of film strength (break elongation)]
  • a negative curable composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a negative curable composition layer.
  • Example 19 it was applied on a silicon wafer by a slit coating method instead of a spin coating method.
  • the silicon wafer to which the obtained negative curable composition layer is applied is dried on a hot plate at 80 ° C. for 5 minutes, and the negative curable composition having the thickness shown in Table 1 or Table 2 is placed on the silicon wafer. Got a layer.
  • the entire surface of the obtained negative curable composition layer was exposed to i-rays with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).
  • the exposed negative curable composition layer (resin layer) was heated at a heating rate of 10 ° C./min under a nitrogen atmosphere to the temperature described in the “Cure temperature” column of Table 1 or Table 2. After reaching, the temperature was maintained at the temperature described in the "Cure Temperature” column above for the "Cure Time” in Table 1 or Table 2.
  • the cured resin layer (cured film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured film was peeled off from the silicon wafer.
  • the peeled cured film was punched out using a punching machine to prepare a test piece having a sample width of 3 mm and a sample length of 30 mm.
  • the obtained test piece was made of a film in accordance with JIS-K6251 using a tensile tester (Tencilon) at a crosshead speed of 300 mm / min and in an environment of 25 ° C. and 65% RH (relative humidity).
  • the elongation at break in the longitudinal direction was measured.
  • the evaluation was carried out 5 times each, and the arithmetic mean value of the elongation rate (break elongation rate) when the film was broken was used as an index value.
  • Example 19 [Evaluation of solvent resistance]
  • a negative curable composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a negative curable composition layer.
  • Example 19 it was applied on a silicon wafer by a slit coating method instead of a spin coating method.
  • the silicon wafer to which the obtained negative curable composition layer is applied is dried on a hot plate at 80 ° C. for 5 minutes, and the negative curable composition having the thickness shown in Table 1 or Table 2 is placed on the silicon wafer. A layer was formed.
  • the entire surface of the negative curable composition layer on the silicon wafer was exposed to i-rays with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).
  • the exposed negative curable composition layer (resin layer) is heated at a heating rate of 10 ° C./min under a nitrogen atmosphere to the temperature described in the “Cure temperature” column of Table 1 or Table 2. After reaching the temperature, the temperature was maintained at the temperature described in the “Cure temperature” column for the “Cure time” in Table 1 or Table 2, to obtain a cured layer (resin layer) of the negative curable composition layer.
  • the obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
  • Example 19 [Evaluation of adhesion]
  • a negative curable composition or a comparative composition was applied in layers on a copper substrate by a spin coating method to form a negative curable composition layer.
  • Example 19 it was applied on a copper substrate by a slit coating method instead of a spin coating method.
  • the copper substrate to which the obtained negative curable composition layer was applied was dried on a hot plate at 80 ° C. for 5 minutes, and the negative curable composition having the thickness shown in Table 1 or 2 was placed on the copper substrate. A layer was formed.
  • the obtained negative photosensitive composition layer was 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. .. Then, it was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 5 minutes, and after the development, it was washed with pure water for 20 seconds to obtain a 100 ⁇ m square resin layer. Further, in a nitrogen atmosphere, the temperature is raised at a heating rate of 10 ° C./min to reach the temperature described in the “Cure temperature” column of Table 1 or Table 2, and then the “Cure time” in Table 1 or Table 2 is reached. A resin film was obtained by maintaining the temperature described in the above "Cure temperature” column.
  • the shearing force of the obtained resin film was measured using a bond tester (CondorSigma, manufactured by XYZTEC) in an environment of 25 ° C. and 65% relative humidity (RH). Adhesion was evaluated according to the following evaluation criteria. The evaluation results are described in the column of "Evaluation item 3: Adhesion evaluation" in Table 1 or Table 2. It can be said that the larger the shearing force, the better the adhesion of the obtained cured film.
  • the alkali-soluble polyimide, photoradical generator, thermoacid generator, acid cross-linking agent, and solvent having a boiling point higher than the acid generation temperature of the thermoacid generator according to the present invention are included. It can be seen that the negative curable composition in which the content of the solvent is 10% by mass or more with respect to the total mass of the composition is excellent in the film strength of the cured film.
  • the negative curable composition according to Comparative Example 1 does not contain a thermoacid generator.
  • the negative curable compositions according to Comparative Examples 2 and 3 do not contain a solvent having an acid generation temperature of the thermal acid generator at 220 ° C. and a boiling point higher than the acid generation temperature. It can be seen that the negative curable compositions according to Comparative Examples 1 to 3 are inferior in film strength of the 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 substrate 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). Exposure was performed at a wavelength of 365 nm via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m).
  • the mixture was developed with 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 180 ° C., the temperature was maintained at 180 ° 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 properties.
  • 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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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne : une composition durcissable négative qui donne un film durci présentant une excellente résistance de film ; un film durci obtenu par durcissement de la composition durcissable négative ; un produit en couches contenant le film durci ; un procédé de production du film durci ; et un dispositif à semi-conducteur qui comprend le film durci ou le produit en couches. La composition durcissable négative contient un polyimide soluble dans les alcalis, un générateur de photo-radicaux, un générateur d'acide thermique, un agent de réticulation d'acide et un solvant présentant un point d'ébullition supérieur à la température de génération d'acide du générateur d'acide thermique. La teneur en solvant est de 10 % en masse ou plus par rapport à la masse totale de la composition. Le film durci est obtenu par durcissement de la composition durcissable négative. Le produit en couches comprend le film durci. Le procédé de production d'un film durci comprend une étape de formation de film. Le dispositif à semi-conducteur comprend le film durci ou le produit en couches.
PCT/JP2020/019841 2019-06-06 2020-05-20 Composition durcissable négative, film durci, produit en couches, procédé de production de film durci, et dispositif à semi-conducteur WO2020246234A1 (fr)

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JP2021524742A JP7334247B2 (ja) 2019-06-06 2020-05-20 ネガ型硬化性組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス

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JP2019-106283 2019-06-06

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JP (2) JP7334247B2 (fr)
TW (1) TWI836067B (fr)
WO (1) WO2020246234A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004244358A (ja) * 2003-02-13 2004-09-02 Shin Etsu Chem Co Ltd 新規スルホニルジアゾメタン化合物、光酸発生剤、並びにそれを用いたレジスト材料及びパターン形成方法
JP2010210851A (ja) * 2009-03-10 2010-09-24 Toray Ind Inc 感光性樹脂組成物
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
WO2017038664A1 (fr) * 2015-08-31 2017-03-09 富士フイルム株式会社 Composition, film durci, procédé de fabrication d'un film durci, procédé de fabrication d'un dispositif semi-conducteur et dispositif semi-conducteur
WO2018047688A1 (fr) * 2016-09-09 2018-03-15 東レ株式会社 Composition de résine

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004258070A (ja) * 2003-02-24 2004-09-16 Sumitomo Chem Co Ltd ポジ型感光性組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004244358A (ja) * 2003-02-13 2004-09-02 Shin Etsu Chem Co Ltd 新規スルホニルジアゾメタン化合物、光酸発生剤、並びにそれを用いたレジスト材料及びパターン形成方法
JP2010210851A (ja) * 2009-03-10 2010-09-24 Toray Ind Inc 感光性樹脂組成物
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
WO2017038664A1 (fr) * 2015-08-31 2017-03-09 富士フイルム株式会社 Composition, film durci, procédé de fabrication d'un film durci, procédé de fabrication d'un dispositif semi-conducteur et dispositif semi-conducteur
WO2018047688A1 (fr) * 2016-09-09 2018-03-15 東レ株式会社 Composition de résine

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TW202107204A (zh) 2021-02-16
JP7334247B2 (ja) 2023-08-28
JP2023104958A (ja) 2023-07-28
TWI836067B (zh) 2024-03-21

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