Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
  • C08F290/145—Polyamides; Polyesteramides; Polyimides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
• • 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
• • 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
• • 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
  • C08G73/22—Polybenzoxazoles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; 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
  • 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
  • G03F7/20—Exposure; Apparatus therefor

Definitions

• the present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, and a semiconductor device.
• Cyclic resin such as polyimide is applied to various applications because it has excellent heat resistance and insulating properties.
• the application is not particularly limited, and examples thereof include a semiconductor device for mounting as a material for an insulating film or a sealing material, or a protective film. It is also used as a base film and coverlay for flexible substrates.
• the cyclized resin such as polyimide is used in the form of a cyclized resin such as polyimide and a resin composition containing at least one of the precursors of the cyclized resin.
• a resin composition is applied to a base material by, for example, coating to form a photosensitive film, and then exposed, developed, heated or the like, if necessary, to form a cured product on the base material.
• the precursor of the cyclized resin such as the polyimide precursor is cyclized by heating, for example, and becomes a cyclized resin such as polyimide in the cured product.
• the resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the applied resin composition at the time of application. It can be said that it is excellent in sex.
• the above-mentioned resin compositions are expected to be increasingly applied in industry from the viewpoint of excellent manufacturing adaptability.
• Patent Document 1 describes (a) a polymer (A) containing a specific structural unit as a main component, (b) a compound (B) having a specific structure, and (c) a photoinitiator and / or a sensitizer.
• a photosensitive polyimide precursor composition comprising and / or a photoreactive polymer has been described.
• Patent Document 2 describes (A) a polyimide precursor having a specific structural unit: 100 parts by mass, (B) a photopolymerization initiator: 1 to 20 parts by mass, and (C) a compound represented by a specific structure.
• a negative photosensitive resin composition containing at least one compound selected from the group consisting of a polymer thereof and a compound represented by a specific structure, or a polymer thereof, or a polymer thereof: 0.1 to 30 parts by mass. The thing is listed.
• the present invention relates to a resin composition for obtaining a cured product having excellent chemical resistance, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and the curing. It is an object of the present invention to provide a semiconductor device including a thing or the above-mentioned laminate.
• the radically polymerizable compound contains compound A having a urea bond and no axis of symmetry.
• the compound A is a resin composition that satisfies at least one of the following conditions 1 and 2.
• Condition 1 Compound A has two or more radically polymerizable groups
• Condition 2 Compound A has at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group and a cyano group.
• the cyclized resin or its precursor is at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor.
• ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the acid value of the cyclized resin or its precursor is 0 mmol / g to 1.2 mmol / g.
• ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the compound A contains an aromatic group.
• ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, further comprising a compound different from the compound A as the radically polymerizable compound.
• ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the compound A is a compound represented by the following formula (1-1) or formula (1-2).
• RP1 and RP2 each independently represent a group containing at least one radically polymerizable group;
• RP1 represents a group containing at least one radically polymerizable group, and L3 represents a divalent linking group.
• ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 5>, which is used for forming an interlayer insulating film for a rewiring layer.
• ⁇ 8> A cured product obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 7>.
• ⁇ 9> A laminated body containing two or more layers made of the cured product according to ⁇ 8> and containing a metal layer between any of the layers made of the cured product.
• a method for producing a cured product which comprises a film forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 7> onto a substrate to form a film.
• ⁇ 11> The method for producing a cured product according to ⁇ 10>, which comprises an exposure step of selectively exposing the film and a developing step of developing the film with a developer to form a pattern.
• ⁇ 12> The method for producing a cured product according to ⁇ 10> or ⁇ 11>, which comprises a heating step of heating the film at 50 to 450 ° C.
• a semiconductor device comprising the cured product according to ⁇ 8> or the laminate according to ⁇ 9>.
• a resin composition for obtaining a cured product having excellent chemical resistance, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and a method for producing the cured product is provided.
• the present invention is not limited to the specified embodiments.
• the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
• the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.
• the notation not describing substitution and non-substitution 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, unless otherwise specified. 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.
• Any, and “(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 values measured by gel permeation chromatography (GPC) method and are defined as polystyrene-equivalent values unless otherwise specified.
• GPC 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 connecting and using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series.
• the molecular weights shall be measured using THF (tetrahydrofuran) as an eluent.
• NMP N-methyl-2-pyrrolidone
• the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
• UV rays ultraviolet rays
• a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other.
• the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as "upper”. And the opposite direction is called "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "up" direction in the present specification may be different from the vertical upward direction.
• the composition may contain, as each component contained in the composition, two or more kinds of compounds corresponding to the component.
• the content of each component in the composition means the total content of all the compounds corresponding to the component.
• the temperature is 23 ° C.
• the atmospheric pressure is 101,325 Pa (1 atmospheric pressure)
• the relative humidity is 50% RH.
• a combination of preferred embodiments is a more preferred embodiment.
• the resin composition of the present invention contains a cyclized resin or a precursor thereof, a radical polymerization initiator, and a radically polymerizable compound, and the radically polymerizable compound has a urea bond and does not have an axis of symmetry.
• the above-mentioned compound A satisfies at least one of the following conditions 1 and 2.
• Condition 1 Compound A has two or more radically polymerizable groups.
• Condition 2 Compound A has at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group and a cyano group.
• the resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to exposure and development, and may be used for exposure and formation of a film to be subjected to development using a developing solution containing an organic solvent.
• the resin composition of the present invention can be used, for example, for forming an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like, and can be used for forming an interlayer insulating film for a rewiring layer.
• the resin composition of the present invention may be used for forming a photosensitive film to be subjected to negative type development.
• negative-type development refers to development in which a non-exposed portion is removed by development in exposure and development
• positive-type development refers to development in which an exposed portion is removed by development.
• the exposure method, the developer, and the developing method include, for example, the exposure method described in the exposure step in the description of the method for producing a cured product described later, the developer and the developing method described in the developing step. Is used.
• a radically polymerizable compound having a urea bond For compositions containing a cyclized resin or a precursor thereof, the use of a radically polymerizable compound having a urea bond has been studied in the prior art. However, when a radically polymerizable compound having a urea bond is used in a resin composition containing a cyclized resin or a precursor thereof, the radically polymerizable compounds are likely to aggregate with each other, so that the chemical resistance may decrease. There was. In particular, a polymerizable compound having two or more radically polymerizable groups and having a urea bond, or having a polar group such as a hydroxy group, an alkyleneoxy group, an amide group or a cyano group and having a urea bond.
• the polymerizable compound tends to aggregate, and if it is polymerized after being formed into a composition film, the density of the polymer in the film may become uneven and the chemical resistance may be lowered. Therefore, as a result of diligent studies by the present inventors, a polymerizable compound having two or more radically polymerizable groups and having a urea bond, or a polar group such as a hydroxy group, an alkyleneoxy group, an amide group, or a cyano group was found. It was found that the chemical resistance is improved by using the compound A, which is a compound having no axis of symmetry, as the polymerizable compound having a urea bond.
• the compound A does not have an axis of symmetry, aggregation is suppressed as described above, so that the solubility in the developing solution in the unexposed portion of the film is improved, and it is considered that the developability is excellent. Further, since the aggregation of the compound A is suppressed as described above, for example, the ring closure of the precursor of the cyclized resin is suppressed from being inhibited by the polymer of the aggregated polymerizable compound, and the resulting cured film is stretched at break. Is also presumed to be excellent.
• Patent Documents 1 and 2 do not describe the use of compound A.
• the resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of a cyclized resin and a precursor thereof.
• the cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.
• the main chain represents the relatively longest bound chain in the resin molecule.
• the cyclization resin include polyimide, polybenzoxazole, and polyamideimide.
• the precursor of the cyclized resin refers to a resin that changes its chemical structure due to an external stimulus and becomes a cyclized resin, and a resin that changes its chemical structure due to heat and becomes a cyclized resin is preferable, and a ring closure reaction occurs due to heat.
• a resin that becomes a cyclized resin by forming a ring structure is more preferable.
• the precursor of the cyclization resin include a polyimide precursor, a polybenzoxazole precursor, a polyamide-imide precursor and the like. That is, the resin composition of the present invention is at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor as the specific resin. It is preferable to contain a resin (specific resin).
• the resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin.
• the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
• the resin composition of the present invention preferably contains a radical cross-linking agent described later. Further, if necessary, a sensitizer described later can be included. From such a resin composition of the present invention, for example, a negative photosensitive film is formed.
• the specific resin has a polymerizable group, it is also preferable that the resin has a molecular chain containing a polymerizable group and a urea bond. The molecular chain is preferably bonded to the main chain of the resin as a side chain, for example.
• the molecular chain may be, for example, of R 111 , R 115 , R 113 and R 114 in the repeating unit represented by the formula (2). It is preferably contained in at least one.
• the molecular chain is contained in at least one of R 131 and R 132 in the repeating unit represented by the formula (4), for example. Is preferable.
• the molecular chain may be, for example, of R 121 , R 122 , R 123 and R 124 in the repeating unit represented by the formula (3).
• the molecular chain is contained in at least one of R 133 and R 134 in the repeating unit represented by the formula (X), for example. Is preferable.
• the specific resin contains a repeating unit represented by the formula (PAI-2) described later, the molecular chain is, for example, R 111 , R 117 and R 113 in the repeating unit represented by the formula (PAI-2). It is preferable that it is contained in at least one of.
• the molecular chain is, for example, at least one of R 111 and R 117 in the repeating unit represented by the formula (PAI-3). It is preferably contained in one.
• the acid value of the specific resin is preferably 0 mmol / g to 1.2 mmol / g, more preferably 0 mmol / g to 0.8 mmol / g, and 0 mmol / g to 0 mmol / g. It is more preferably 0.6 mmol / g.
• the acid value is measured, for example, by the method described in JIS K 0070: 1992.
• the polyimide precursor used in the present invention is not particularly specified, such as its type, but preferably contains a repeating unit represented by the following formula (2).
• a 1 and A 2 independently represent an oxygen atom or -NH-
• R 111 represents a divalent organic group
• R 115 represents a tetravalent organic group
• R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
• a 1 and A 2 in the formula (2) independently represent an oxygen atom or —NH—, and an oxygen atom is preferable.
• R 111 in the formula (2) represents a divalent organic group.
• the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms are exemplified.
• a cyclic aliphatic group having 3 to 20, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
• the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a hetero atom. It may be substituted with a group containing.
• Preferred embodiments of the present invention are exemplified by the groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably the groups represented by -Ar-L-Ar-.
• Ar is an aromatic group independently
• L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, —O—, —CO. -, -S-, -SO 2- or -NHCO-, or a group consisting of a combination of two or more of the above.
• R 111 is preferably derived from diamine.
• the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used. Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof. It is preferably a diamine containing, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms.
• the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the hydrocarbon group of the ring member is a hetero atom. It may be substituted with a containing group.
• groups containing aromatic groups include:
• * represents a binding site with another structure.
• diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 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; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl;
• diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferable.
• a diamine having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 is also preferably used.
• R 111 is preferably represented by ⁇ Ar—L—Ar— from the viewpoint of the flexibility of the obtained organic film.
• Ar is an aromatic group independently
• L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , -SO 2- or -NHCO-, or a group consisting of a combination of two or more of the above.
• Ar is preferably a phenylene group
• L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— or —SO2- . ..
• the aliphatic hydrocarbon group here is preferably an alkylene group.
• R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61).
• a divalent organic group represented by the formula (61) is more preferable.
• Equation (51) In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoro. It is a methyl group, and each of * independently represents a bonding site with a nitrogen atom in the formula (2).
• the monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
• R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is an independent binding site with a nitrogen atom in formula (2). show.
• Examples of the diamine giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, and 2,2'-bis. (Fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like can be mentioned. These may be used alone or in combination of two or more.
• R 115 in the formula (2) represents a tetravalent organic group.
• a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
• * independently represents a binding site with another structure.
• R 112 is a single-bonded or divalent linking group, which may be substituted with a single-bonded or fluorine atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, —O—, -CO-, -S-, -SO 2- , and -NHCO-, and a group selected from a combination thereof are preferable, and a single bond may be substituted with a fluorine atom having 1 to 1 to carbon atoms.
• it is a group selected from 3 alkylene groups, -O-, -CO-, -S- and -SO 2- , and -CH 2- , -C (CF 3 ) 2- , -C ( CH 3 ) It is more preferably a divalent group selected from the group consisting of 2-, -O-, -CO-, -S- and -SO 2- .
• R 115 include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic acid dianhydride.
• the polyimide precursor may contain only one type of tetracarboxylic acid dianhydride residue or two or more types as a structure corresponding to R 115 .
• the tetracarboxylic acid dianhydride is preferably represented by the following formula (O).
• R 115 represents a tetravalent organic group.
• the preferred range of R 115 is synonymous with R 115 in the formula (2), and the preferred range is also the same.
• tetracarboxylic acid dianhydride examples include pyromellitic acid dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-.
• PMDA pyromellitic acid dianhydride
• 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride 3,3', 4,4'-.
• tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also mentioned as preferable examples.
• R 111 and R 115 has an OH group. More specifically, as R 111 , a residue of a bisaminophenol derivative can be mentioned.
• R 113 and R 114 in the formula (2) independently represent a hydrogen atom or a monovalent organic group, respectively.
• the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
• at least one of R 113 and R 114 contains a polymerizable group, and it is more preferable that both contain a polymerizable group.
• at least one of R 113 and R 114 contains two or more polymerizable groups.
• the polymerizable group a radically polymerizable group is preferable because it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals and the like.
• the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group and an amino group. Be done.
• a group having an ethylenically unsaturated bond is preferable.
• Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to the vinyl group (for example, a vinylphenyl group), and a (meth) acrylamide group.
• R200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and a hydrogen atom or a methyl group is preferable.
• * represents a binding site with another structure.
• R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH (OH) CH 2- , a cycloalkylene group or a polyalkyleneoxy group.
• R 201 examples include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group, 1,2-butanjiyl group, 1, 3-Butanjiyl group, -CH 2 CH (OH) CH 2- , polyalkyleneoxy group, alkylene group such as ethylene group, propylene group, -CH 2 CH (OH) CH 2- , cyclohexyl group, polyalkylene An oxy group is more preferable, and an alkylene group such as an ethylene group and a propylene group, or a polyalkylene oxy group is further preferable.
• alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group and dodecamethylene group, 1,2-butanjiyl group, 1, 3-Butanjiyl group,
• the polyalkyleneoxy group refers to a group to which two or more alkyleneoxy groups are directly bonded.
• the alkylene group in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
• the sequence of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
• the carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6.
• the alkylene group may have a substituent.
• Preferred substituents include alkyl groups, aryl groups, halogen atoms and the like.
• the number of alkyleneoxy groups contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
• the polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethylethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance.
• a group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable.
• the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.
• R 113 is a hydrogen atom or R 114 is a hydrogen atom
• R 113 is a hydrogen atom
• R 114 is a hydrogen atom
• the polyimide precursor forms a salt with a tertiary amine compound having an ethylenically unsaturated bond.
• the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
• R 113 and R 114 may be a polar conversion group such as an acid-degradable group.
• the acid-degradable group is not particularly limited as long as it decomposes by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group or a silyl ether group.
• a tertiary alkyl ester group or the like is preferable, and an acetal group or a ketal group is more preferable from the viewpoint of exposure sensitivity.
• the acid-degradable group examples include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group and tert-butoxycarbonylmethyl.
• examples include a group, a trimethylsilyl ether group and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.
• the polyimide precursor has a fluorine atom in its structure.
• the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.
• the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
• the diamine an embodiment using bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like can be mentioned.
• the repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by the formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude. Equation (2-A) In formula (2-A), A 1 and A 2 represent oxygen atoms, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each independently. Representing a hydrogen atom or a monovalent organic group, at least one of R 113 and R 114 is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.
• a 1 , A 2 , R 111 , R 113 , and R 114 are independently synonymous with A 1 , A 2 , R 111 , R 113 , and R 114 in the formula (2), and the preferred ranges are also the same. .. R 112 has the same meaning as R 112 in the formula (5), and the preferred range is also the same.
• the polyimide precursor may contain one kind of repeating unit represented by the formula (2), but may contain two or more kinds. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the polyimide precursor may contain other types of repeating units in addition to the repeating units of the above formula (2).
• the content of the repeating unit represented by the formula (2) is 50 mol% or more of all the repeating units.
• the total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%.
• the upper limit of the total content is not particularly limited, and all the repeating units in the polyimide precursor except the terminal may be the repeating unit represented by the formula (2).
• the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000.
• the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
• the degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more.
• the upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less.
• the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
• the resin composition contains a plurality of types of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion of at least one type of polyimide precursor are in the above range. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of polyimide precursors as one resin are within the above ranges.
• the polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide that is soluble in a developing solution containing an organic solvent as a main component.
• 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 formability.
• a polyimide that dissolves is preferable, and a polyimide that dissolves 1.0 g or more is more preferable.
• the upper limit of the dissolution amount is not particularly limited, but is preferably 100 g or less.
• the polyimide is preferably a polyimide having a plurality of imide structures in the main chain from the viewpoint of the film strength and the insulating property of the obtained organic film.
• the "main chain” refers to the relatively longest bound chain among the molecules of the polymer compound constituting the resin, and the “side chain” refers to other bound chains.
• the polyimide has a fluorine atom.
• the fluorine atom is preferably contained in, for example, R 132 in the repeating unit represented by the formula (4) described later, or R 131 in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula (4) described later. It is more preferable that it is contained as an alkyl fluoride group in R 132 in the repeating unit represented by 4) or in R 131 in the repeating unit represented by the formula (4) described later.
• the amount of fluorine atoms with respect to the total mass of the polyimide is preferably 5% by mass or more, and preferably 20% by mass or less.
• the polyimide has a silicon atom.
• the silicon atom is preferably contained in R 131 in the repeating unit represented by the formula (4) described later, and is organically modified (poly) in R 131 in the repeating unit represented by the formula (4) described later. ) It is more preferable that it is contained as a siloxane structure. Further, the silicon atom or the organically modified (poly) siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
• the amount of silicon atoms with respect to the total mass of the polyimide is preferably 1% by mass or more, more preferably 20% by mass or less.
• the polyimide preferably has an ethylenically unsaturated bond.
• the polyimide may have an ethylenically unsaturated bond at the end of the main chain or at the side chain, but it is preferable to have it at the side chain.
• the ethylenically unsaturated bond is preferably radically polymerizable.
• the ethylenically unsaturated bond is preferably contained in R 132 in the repeating unit represented by the formula (4) described later or R 131 in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula described later.
• R 132 in the repeating unit represented by (4) or R 131 in the repeating unit represented by the formula (4) described later is contained as a group having an ethylenically unsaturated bond.
• the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by the formula (4) described later, and ethylene is contained in R 131 in the repeating unit represented by the formula (4) described later. It is more preferably contained as a group having a sex unsaturated bond.
• Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and 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 (IV).
• R20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and a hydrogen atom or a methyl group is preferable.
• (Poly) alkyleneoxy 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 alkylene group having 2 to 12 carbon atoms may be a linear group, a branched chain, a cyclic group, or an alkylene group represented by a combination thereof.
• an alkylene group having 2 to 12 carbon atoms an alkylene group having 2 to 8 carbon atoms is preferable, and an alkylene group having 2 to 4 carbon atoms is more preferable.
• R 21 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) alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded
• X Indicates an oxygen atom or a sulfur atom
• * represents a bond site with another structure
• ⁇ represents a bond site with an oxygen atom to which R 21 in the formula (IV) is bonded.
• a preferred embodiment of the alkylene group having 2 to 12 carbon atoms in L or the (poly) alkyleneoxy group having 2 to 30 carbon atoms is the above-mentioned R 21 having 2 to 12 carbon atoms. This is the same as the preferred embodiment of the alkylene group of 12 or the (poly) alkyleneoxy group having 2 to 30 carbon atoms.
• X is preferably an oxygen atom.
• * is synonymous with * in the formula (IV), and the preferred embodiment is also the same.
• the structure represented by the formula (R1) comprises, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group and a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). Obtained by reacting.
• the structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
• the structure represented by the formula (R3) is formed 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 polyimide is preferably 0.0001 to 0.1 mol / g, more preferably 0.0005 to 0.05 mol / g.
• the polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
• examples of the polymerizable group other than the group having an 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. It is preferable that the polymerizable group other than the group having an ethylenically unsaturated bond is contained in R 131 in the repeating unit represented by the formula (4) described later, for example.
• the amount of the polymerizable group other than the group having an ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and preferably 0.001 to 0.05 mol / g. More preferred.
• the polyimide may have a polar conversion group such as an acid-decomposable group.
• the acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R 113 and R 114 in the above formula (2), and the preferred embodiment is also the same.
• the polarity converting group is contained in, for example, R 131 , R 132 , the end of polyimide, or the like in the repeating unit represented by the formula (4) described later.
• the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 mgKOH / g or more from the viewpoint of improving developability. Is more preferable.
• 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 of the polyimide is preferably 1 to 35 mgKOH / g, and 2 to 30 mgKOH. / G is more preferable, and 5 to 20 mgKOH / g is even more preferable.
• the acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
• the acid value of the polyimide is preferably 0 mmol / g to 1.2 mmol / g, more preferably 0 mmol / g to 0.8 mmol / g, and 0 mmol / g to 0. It is more preferably 0.6 mmol / g.
• the acid group contained in the polyimide 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 acid group is a polyvalent acid such as phosphoric acid
• the above pKa is the first dissociation constant.
• the 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 polyimide preferably has a phenolic hydroxy group.
• the polyimide may have a phenolic hydroxy group at the end of the main chain or at the side chain.
• the phenolic hydroxy group is preferably contained in, for example, R 132 in the repeating unit represented by the formula (4) described later or R 131 in the repeating unit represented by the formula (4) described later.
• the amount of the phenolic hydroxy group with respect to the total mass of the polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.
• the polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but preferably contains a repeating unit represented by the following formula (4).
• R 131 represents a divalent organic group and R 132 represents a tetravalent organic group.
• the polymerizable group may be located at at least one of R 131 and R 132 , or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2). It may be located in.
• Equation (4-2) At least one of R 134 and R 135 is a polymerizable group, when it is not a polymerizable group, it is an organic group, and the other group is synonymous with the formula (4).
• Examples of the polymerizable group include a group containing the above-mentioned ethylenically unsaturated bond and a crosslinkable group other than the above-mentioned group having an ethylenically unsaturated bond.
• R 131 represents a divalent organic group.
• the divalent organic group the same group as R 111 in the formula (2) is exemplified, and the preferable range is also the same.
• examples of R 131 include diamine residues remaining after removal of the amino group of diamine.
• Examples of the diamine include aliphatic, cyclic aliphatic or aromatic diamines. Specific examples include the example of R 111 in the formula (2) of the polyimide precursor.
• R 131 is a diamine residue having at least two alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the generation of warpage during firing. More preferably, it is a diamine residue containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule, and more preferably, the above diamine, which does not contain an aromatic ring. Is.
• Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include Jeffamine® KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) Examples thereof include, but are not limited to, propoxy) propane-2-amine and 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propane-2-amine.
• R 132 represents a tetravalent organic group.
• the tetravalent organic group the same group as R 115 in the formula (2) is exemplified, and the preferable range is also the same.
• examples of R 132 include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic acid dianhydride. Specific examples include the example of R 115 in the formula (2) of the polyimide precursor. From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
• R 131 and R 132 It is also preferable to have an OH group in at least one of R 131 and R 132 . More specifically, as R 131 , 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2- Bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the above (DA-1) to (DA-18) are preferred examples. As R 132 , the above-mentioned (DAA-1) to (DAA-5) are more preferable examples.
• the polyimide has a fluorine atom in its structure.
• the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.
• the polyimide may be copolymerized with an aliphatic group having a siloxane structure.
• the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
• the main chain end of the polyimide is sealed with an end-sealing agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, and monoactive ester compound. It is preferable to have. Of these, it is more preferable to use monoamine, and preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7.
• an end-sealing agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, and monoactive ester compound. It is preferable to have. Of these, it is more preferable to use monoamine, and preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7.
• the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, the insulating property, etc. of the obtained organic film. More preferably, it is 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, for example, by the following method. The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near 1377 cm -1 , which is the absorption peak derived from the imide structure. Next, the polyimide is heat-treated at 350 ° C.
• the polyimide may include a repeating unit represented by the above formula (4), all containing one type of R 131 or R 132 , and the above formula including two or more different types of R 131 or R 132 . It may include the repeat unit represented by 4). Further, the polyimide may contain other types of repeating units in addition to the repeating unit represented by the above formula (4). Examples of the other type of repeating unit include the repeating unit represented by the above-mentioned equation (2).
• the polyimide is, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine (partially replaced with a terminal encapsulant which is a monoamine) at a low temperature, or a tetracarboxylic acid dianhydride (partly an acid anhydride) at a low temperature.
• a method such as a method of reacting with a terminal encapsulant) is used to obtain a polyimide precursor, which is completely imidized using a known imidization reaction method, or an imidization reaction in the middle. It can be synthesized by using the method of introducing a partially imidized structure, and further, by blending the completely imidized polymer with the polyimide precursor thereof, the method of introducing a partially imidized structure is used. .. Further, other known polyimide synthesis methods can also be applied.
• the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties (for example, elongation at break), the weight average molecular weight is particularly preferably 15,000 or more.
• the number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and further preferably 4,000 to 20,000.
• the degree of dispersion of the molecular weight of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more.
• the upper limit of the dispersity of the molecular weight of the polyimide is not particularly determined, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less.
• the weight average molecular weight, the number average molecular weight, and the degree of dispersion of at least one type of polyimide are in the above range. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of polyimides as one resin are each within the above ranges.
• the polybenzoxazole precursor used in the present invention is not particularly defined for its structure and the like, but preferably contains a repeating unit represented by the following formula (3).
• R 121 represents a divalent organic group
• R 122 represents a tetravalent organic group
• R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group. show.
• R 123 and R 124 are synonymous with R 113 in the formula (2), respectively, and the preferable range is also the same. That is, at least one is preferably a polymerizable group.
• R 121 represents a divalent organic group.
• the divalent organic group a group containing at least one of an aliphatic group and an aromatic group is preferable.
• the aliphatic group a linear aliphatic group is preferable.
• R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
• a dicarboxylic acid residue a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
• a dicarboxylic acid containing an aliphatic group a dicarboxylic acid containing a linear or branched (preferably straight chain) aliphatic group is preferable, and a linear or branched (preferably straight chain) aliphatic group and two -COOH are preferable.
• a dicarboxylic acid consisting of is more preferable.
• the number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, and 4 to 20. It is more preferably 15, and particularly preferably 5 to 10.
• the linear aliphatic group is preferably an alkylene group.
• dicarboxylic acid containing a linear aliphatic group examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-Didimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimeric acid, sverin Acid, dodecafluorosveric acid, azelaic acid, sebacic acid, s
• Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).
• dicarboxylic acid containing an aromatic group a dicarboxylic acid having the following aromatic groups is preferable, and a dicarboxylic acid consisting of only a group having the following aromatic groups and two -COOH is more preferable.
• A is -CH 2- , -O-, -S-, -SO 2- , -CO-, -NHCO-, -C (CF 3 ) 2- , and -C (CH 3 ) 2- It represents a divalent group selected from the group consisting of, and * represents a binding site with another structure independently.
• dicarboxylic acid containing an aromatic group examples include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.
• R 122 represents a tetravalent organic group.
• the tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferable range is also the same.
• R 122 is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'.
• bisaminophenol derivatives having the following aromatic groups are preferable.
• X 1 represents -O-, -S-, -C (CF 3 ) 2- , -CH 2- , -SO 2- , -NHCO-, and * and # represent other structures, respectively.
• R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Further, it is also preferable that R 122 has a structure represented by the above formula.
• any two of the four * and # in total are the bonding sites with the nitrogen atom to which R 122 in the formula (3) is bonded, and The other two are preferably the bonding sites with the oxygen atom to which R 122 in the formula (3) is bonded, and the two * are the bonding sites with the oxygen atom to which the R 122 in the formula (3) is bonded.
• two # are the bonding sites with the nitrogen atom to which R 122 in the formula (3) is bonded, or two * are the bonding sites with the nitrogen atom to which R 122 in the formula (3) is bonded.
• the site is a site and the two #s are the bonding sites with the oxygen atom to which the R 122 in the formula (3) is bonded, and the two * are the oxygen to which the R 122 in the formula (3) is bonded. It is more preferable that it is a bond site with an atom and the two #s are bond sites with a nitrogen atom to which R 122 in the formula (3) is bonded.
• the bisaminophenol derivative is also preferably a compound represented by the formula (As).
• R 1 is a hydrogen atom, an alkylene, a substituted alkylene, -O-, -S-, -SO 2- , -CO-, -NHCO-, a single bond, or the following formula (A-). It is an organic group selected from the group of sc).
• R 2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
• R 3 is any of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
• R3 having a substituent at the ortho position of the phenolic hydroxy group , that is, R3 is considered to bring the distance between the carbonyl carbon of the amide bond and the hydroxy group closer, and at a low temperature. It is particularly preferable in that the effect of increasing the cyclization rate when cured is further enhanced.
• R 2 is an alkyl group and R 3 is an alkyl group has high transparency to i-rays and a high cyclization rate when cured at a low temperature. The effect can be maintained, which is preferable.
• R 1 is an alkylene or a substituted alkylene.
• the alkylene and the substituted alkylene according to R 1 include linear or branched alkyl groups having 1 to 8 carbon atoms, among which -CH 2- and -CH (CH 3 ).
• -, -C (CH 3 ) 2 has sufficient solubility in a solvent while maintaining the effects of high transparency to i-rays and high cyclization rate when cured at low temperature. It is more preferable in that an excellent polybenzoxazole precursor can be obtained.
• the polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units of the above formula (3).
• the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that the generation of warpage associated with ring closure can be suppressed.
• Z has an a structure and a b structure
• R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
• R 2s is a hydrocarbon group having 1 to 10 carbon atoms.
• at least one of R 3s , R 4s , R 5s , and R 6s is an aromatic group
• the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different.
• the polymerization of the a structure and the b structure may be block polymerization or random polymerization.
• the mol% of the Z portion is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a + b.
• preferred Z includes those in which R 5s and R 6s in the b structure are phenyl groups.
• the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000.
• the tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic acid dianhydride is further contained as the repeating unit.
• the repeating unit Is also preferable.
• examples of such a tetracarboxylic acid residue include the example of R 115 in the formula (2).
• the weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, still more preferably 22,000 to 28, It is 000.
• the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
• the degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, still more preferably 1.6 or more.
• the upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly determined, but for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is further preferable, and 2.3 or less. Is more preferable, and 2.2 or less is even more preferable.
• the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polybenzoxazole precursor may be within the above ranges. preferable. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of polybenzoxazole precursors as one resin are within the above ranges.
• the polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X). It is more preferable that the compound has a polymerizable group. As the polymerizable group, a radically polymerizable group is preferable.
• R 133 represents a divalent organic group and R 134 represents a tetravalent organic group.
• the polymerizable group When having a polymerizable group, the polymerizable group may be located at at least one of R 133 and R 134 , and may be polybenzoxazole as shown in the following formula (X-1) or formula (X-2). It may be located at the end of. Equation (X-1) In the formula (X-1), at least one of R 135 and R 136 is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group is synonymous with the formula (X). Equation (X-2) In formula (X-2), R 137 is a polymerizable group, the other is a substituent, and the other group is synonymous with formula (X).
• the polymerizable group is synonymous with the polymerizable group described in the above-mentioned polymerizable group possessed by the polyimide precursor.
• R 133 represents a divalent organic group.
• the divalent organic group include an aliphatic group and an aromatic group.
• Specific examples include the example of R 121 in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that of R 121 .
• R 134 represents a tetravalent organic group.
• the tetravalent organic group include R 122 in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that of R 122 .
• four conjugates of a tetravalent organic group exemplified as R 122 combine with a nitrogen atom and an oxygen atom in the above formula (X) to form a fused ring.
• R 134 when R 134 is the following organic group, it forms the following structure.
• * represents a binding site with a nitrogen atom or an oxygen atom in the formula (X), respectively.
• the oxazole formation rate of polybenzoxazole is preferably 85% or more, more preferably 90% or more.
• the upper limit is not particularly limited and may be 100%.
• the oxazole formation rate is measured, for example, by the following method.
• the infrared absorption spectrum of polybenzoxazole is measured to determine the peak intensity Q1 near 1650 cm -1 , which is the absorption peak derived from the amide structure of the precursor. Next, normalize by the absorption intensity of the aromatic ring found near 1490 cm -1 .
• the polybenzoxazole may contain a repeating unit of the above formula (X), all comprising one R 131 or R 132 , and the above formula (X) comprising two or more different types of R 131 or R 132 . ) May be included. Further, the polybenzoxazole may contain other types of repeating units in addition to the repeating units of the above formula (X).
• the polybenzoxazole is obtained by reacting, for example, a bisaminophenol derivative with a dicarboxylic acid containing R133 or a compound selected from the dicarboxylic acid dichloride and the dicarboxylic acid derivative of the above dicarboxylic acid to obtain a polybenzoxazole precursor.
• This can be obtained by oxazole using a known oxazole reaction method.
• an active ester-type dicarboxylic acid derivative that has been previously reacted with 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield or the like.
• the weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, still more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one kind of polybenzoxazole is in the above range.
• the number average molecular weight (Mn) of polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. be.
• the degree of dispersion of the molecular weight of the polybenzoxazole is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more.
• the upper limit of the dispersity of the molecular weight of polybenzoxazole is not particularly defined, but for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is further preferable, and 2.3 or less is further preferable. Preferably, 2.2 or less is even more preferable.
• the weight average molecular weight, the number average molecular weight, and the dispersity of at least one type of polybenzoxazole are in the above range. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of polybenzoxazole as one resin are each within the above ranges.
• the polyamide-imide precursor preferably contains a repeating unit represented by the following formula (PAI-2).
• PAI-2 R 117 represents a trivalent organic group
• R 111 represents a divalent organic group
• a 2 represents an oxygen atom or -NH-
• R 113 represents a hydrogen atom or monovalent. Represents an organic group of.
• R 117 is composed of a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroarophatic group, or a single bond or a linking group.
• Examples of the above-mentioned linked groups are a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 6 to 20 carbon atoms.
• the aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable.
• a group in which two or more of the above are combined is more preferable.
• a group is preferable, and an —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
• an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
• halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
• the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
• the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom.
• preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
• arylene group a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
• R 117 is derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. Chlorination is preferable as the halogenation.
• a compound having three carboxy groups is referred to as a tricarboxylic acid compound. Of the three carboxy groups of the tricarboxylic acid compound, two carboxy groups may be acid anhydrideized.
• the halogenated tricarboxylic acid compound used in the production of the polyamide-imide precursor include branched chain aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. Only one kind of these tricarboxylic acid compounds may be used, or two or more kinds may be used.
• the tricarboxylic acid compound includes 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.
• a tricarboxylic acid compound containing 6 to 20 aromatic groups or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or carbon by a single bond or a linking group is preferable.
• a tricarboxylic acid compound containing a group in which two or more aromatic groups of the number 6 to 20 are combined is more preferable.
• the tricarboxylic acid compound examples include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid.
• (Or phthalic acid anhydride) and benzoic acid are single-bonded, -O-, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- or a phenylene group. Examples thereof include linked compounds. These compounds may be compounds in which two carboxy groups are anhydrated (eg, trimellitic acid anhydride) or compounds in which at least one carboxy group is halogenated (eg, trimellitic acid anhydride). There may be.
• R 111 , A 2 , and R 113 are synonymous with R 111 , A 2 , and R 113 in the above formula (2), respectively, and the preferred embodiments are also the same.
• the polyamide-imide precursor may further contain other repeating units.
• the other repeating unit include a repeating unit represented by the above formula (2), a repeating unit represented by the following formula (PAI-1), and the like.
• R 116 represents a divalent organic group and R 111 represents a divalent organic group.
• R 116 is a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroarophatic group, or a single bond or a linking group. Examples of the above-mentioned linked groups are a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 6 to 20 carbon atoms.
• the aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable.
• a group in which two or more of the above are combined is more preferable.
• a group is preferable, and an —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
• an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
• halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
• the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
• the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom.
• preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
• arylene group a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
• R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
• a compound having two carboxy groups is referred to as a dicarboxylic acid compound
• a compound having two halogenated carboxy groups is referred to as a dicarboxylic acid dihalide compound.
• the carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
• Examples of the halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids. Examples include aciddihalide compounds. Only one kind or two or more kinds of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used.
• the dicarboxylic acid compound or the dicarboxylic acid dihalide compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic fat having 3 to 20 carbon atoms.
• a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group group, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms is preferable.
• a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferable.
• dicarboxylic acid compound examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, and methylsuccinic acid, 2,2-.
• R 111 has the same meaning as R 111 in the above formula (2), and the preferred embodiment is also the same.
• the polyamide-imide precursor has a fluorine atom in its structure.
• the fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
• the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure.
• the diamine component an embodiment using bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like can be mentioned.
• a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a repeating unit represented by the formula (2) As one embodiment of the polyamide-imide precursor in the present invention, a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a repeating unit represented by the formula (2).
• An embodiment in which the total content of the units is 50 mol% or more of all the repeating units can be mentioned.
• the total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%.
• the upper limit of the total content is not particularly limited, and all the repeating units in the polyamide-imide precursor except the terminal are represented by the repeating unit represented by the formula (PAI-2) and the formula (PAI-1). It may be either a repeating unit or a repeating unit represented by the formula (2).
• the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) is.
• An embodiment of 50 mol% or more of all repetition units can be mentioned.
• the total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%.
• the upper limit of the total content is not particularly limited, and all the repeating units in the polyamide-imide precursor except the terminal are represented by the repeating unit represented by the formula (PAI-2) or the formula (PAI-1). It may be any of the repeating units to be used.
• the weight average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. ..
• the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
• the degree of dispersion of the molecular weight of the polyamide-imide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
• the upper limit of the dispersity of the molecular weight of the polyamide-imide precursor is not particularly determined, but is preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less, for example.
• the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyamide-imide precursors are preferably in the above range. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of types of polyamide-imide precursors as one resin are within the above ranges.
• the polyamide-imide used in the present invention may be an alkali-soluble polyamide-imide or may be a polyamide-imide soluble in a developer containing an organic solvent as a main component.
• the alkali-soluble polyamide-imide means a polyamide-imide that dissolves 0.1 g or more at 23 ° C. in 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and is 0. It is preferably a polyamide-imide that dissolves 5 g or more, and more preferably a polyamide-imide that dissolves 1.0 g or more.
• the upper limit of the dissolution amount is not particularly limited, but is preferably 100 g or less.
• the polyamide-imide is preferably a polyamide-imide having a plurality of amide bonds and a plurality of imide structures in the main chain from the viewpoint of film strength and insulating property of the obtained organic film.
• the polyamide-imide preferably has a fluorine atom.
• the fluorine atom is preferably contained in, for example, R 117 or R 111 in the repeating unit represented by the formula (PAI-3) described later, and in the repeating unit represented by the formula (PAI-3) described later. It is more preferable that it is contained in R 117 or R 111 as an alkyl fluoride group.
• the amount of fluorine atoms with respect to the total mass of the polyamide-imide is preferably 5% by mass or more, and more preferably 20% by mass or less.
• the polyamide-imide may have an ethylenically unsaturated bond.
• the polyamide-imide may have an ethylenically unsaturated bond at the end of the main chain or at the side chain, but it is preferable to have it at the side chain.
• the ethylenically unsaturated bond is preferably radically polymerizable.
• the ethylenically unsaturated bond is preferably contained in R 117 or R 111 in the repeating unit represented by the formula (PAI-3) described later, and the repeating unit represented by the formula (PAI-3) described later.
• R 117 or R 111 it is more preferable that it is contained as a group having an ethylenically unsaturated bond in R 117 or R 111 in the above.
• the preferred embodiment of the group having an ethylenically unsaturated bond is the same as the preferred embodiment of the group having an ethylenically unsaturated bond in the above-mentioned polyimide.
• the amount of the ethylenically unsaturated bond with respect to the total mass of the polyamide-imide is preferably 0.0001 to 0.1 mol / g, more preferably 0.001 to 0.05 mol / g.
• the polyamide-imide may have a polymerizable group other than the ethylenically unsaturated bond.
• Examples of the polymerizable group other than the ethylenically unsaturated bond in the polyamide-imide include the same groups as the polymerizable group other than the ethylenically unsaturated bond in the above-mentioned polyimide. It is preferable that the polymerizable group other than the ethylenically unsaturated bond is contained in R 111 in the repeating unit represented by the formula (PAI-3) described later, for example.
• the amount of the polymerizable group other than the ethylenically unsaturated bond with respect to the total mass of the polyamide-imide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.
• -Polar conversion group- Polyamideimide may have a polar conversion group such as an acid-degradable group.
• the acid-degradable group in the polyamide-imide is the same as the acid-decomposable group described in R 113 and R 114 in the above formula (2), and the preferred embodiment is also the same.
• the acid value of the polyamide-imide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 mgKOH / g or more, from the viewpoint of improving the developability. It is more preferably 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 of the polyamide-imide is preferably 2 to 35 mgKOH / g. ⁇ 30 mgKOH / g is more preferable, and 5 to 20 mgKOH / g is even more preferable.
• the acid value of the polyamide-imide is preferably 0 mmol / g to 1.2 mmol / g, more preferably 0 mmol / g to 0.8 mmol / g, and 0 mmol / g to 0 mmol / g.
• the acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992. Further, as the acid group contained in the polyamide-imide, the same group as the acid group in the above-mentioned polyimide can be mentioned, and the preferred embodiment is also the same.
• the polyamide-imide preferably has a phenolic hydroxy group.
• the polyamide-imide may have a phenolic hydroxy group at the end of the main chain or at the side chain.
• the phenolic hydroxy group is preferably contained in, for example, R 117 or R 111 in the repeating unit represented by the formula (PAI-3) described later.
• the amount of the phenolic hydroxy group with respect to the total mass of the polyamide-imide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.
• the polyamide-imide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but preferably contains a repeating unit represented by the following formula (PAI-3).
• R 111 and R 117 are synonymous with R 111 and R 117 in formula (PAI-2), respectively, and so are preferred embodiments.
• the polymerizable group may be located at at least one of R 111 and R 117 , or may be located at the end of the polyamide-imide.
• the main chain end of polyamide-imide is sealed with an end sealant such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound.
• an end sealant such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound.
• the preferred embodiment of the terminal encapsulant is the same as the preferred embodiment of the terminal encapsulant in the above-mentioned polyimide.
• the imidization rate (also referred to as "ring closure rate") of the polyamide-imide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, the insulating property, etc. of the obtained organic film. , 90% or more is more preferable.
• the upper limit of the imidization rate is not particularly limited and may be 100% or less.
• the imidization rate is measured by the same method as the ring closure rate of the polyimide described above.
• the polyamide-imide may include a repeating unit represented by the above formula (PAI-3), all comprising one R 111 or R 117 , including two or more different types of R 131 or R 132 . It may contain a repeating unit represented by the above formula (PAI-3). Further, the polyamide-imide may contain other types of repeating units in addition to the repeating units represented by the above formula (PAI-3). Examples of the other type of repeating unit include the repeating unit represented by the above-mentioned formula (PAI-1) or formula (PAI-2).
• a polyamide-imide precursor is obtained by a known method, and the polyamide-imide precursor is completely imidized by using a known imidization reaction method, or the imidization reaction is stopped in the middle and a partial imide structure is obtained.
• the completely imidized polymer By blending the completely imidized polymer with the polyamide-imide precursor thereof, it can be synthesized by utilizing the method of introducing a partially imidized structure.
• the weight average molecular weight (Mw) of the polyamide-imide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, still more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more.
• the number average molecular weight (Mn) of the polyamide-imide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. ..
• the dispersity of the molecular weight of the polyamide-imide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
• the upper limit of the dispersity of the molecular weight of the polyamide-imide is not particularly determined, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less.
• the resin composition contains a plurality of types of polyamide-imides as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion of at least one type of polyamide-imide are in the above ranges. Further, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the plurality of kinds of polyamide-imides as one resin are within the above ranges.
• the polyimide precursor and the like can be, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine at a low temperature, or reacting a tetracarboxylic acid dianhydride with a diamine at a low temperature to obtain a polyamic acid, and a condensing agent or an alkylating agent.
• the remaining dicarboxylic acid can be obtained by acid-halogenizing it with a halogenating agent and reacting it with a diamine.
• a method in which a diester is obtained from tetracarboxylic acid dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid-halogenated with a halogenating agent and reacted with diamine is more preferable.
• Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, Examples thereof include N'-disuccinimidyl carbonate and trifluoroacetic anhydride.
• Examples of the alkylating agent include N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethyl acetal, N, N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate and the like.
• halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.
• an organic solvent in the reaction.
• the organic solvent may be one kind or two or more kinds.
• the organic solvent can be appropriately determined depending on the raw material, but is pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, ⁇ -butyrolactone and the like. Is exemplified.
• the basic compound may be one kind or two or more kinds.
• the basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, N, N-dimethyl-4-amino. Examples thereof include pyridine and the like.
• -End sealant- In the method for producing a polyimide precursor or the like, it is preferable to seal the carboxylic acid anhydride, the acid anhydride derivative, or the amino group remaining at the resin terminal of the polyimide precursor or the like in order to further improve the storage stability.
• examples of the terminal encapsulant include monoalcohol, phenol, thiol, thiophenol, monoamine, etc., and are reactive and stable in the film. From the viewpoint of sex, it is more preferable to use monoalcohol, phenols and monoamine.
• Preferred compounds of monoalcohols include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and flufuryl alcohol, and isopropanol.
• Preferred compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol and hydroxystyrene.
• Preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene and 1-hydroxy-6-.
• Aminonaphthalene 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-amino Naphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4 -Aminobenzene sulfonic acid, 3-amino-4,6-di
• encapsulants for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, anhydrous sulfonic acids, sulfonic acid carboxylic acid anhydrides and the like, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. preferable.
• Preferred compounds for carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornen-2,3-dicarboxylic acid anhydride and the like.
• Preferred compounds for the carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylate chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantancarbonyl chloride. , Heptafluorobutyryl chloride, stearate chloride, benzoyl chloride, and the like.
• the method for producing a polyimide precursor or the like may include a step of precipitating a solid. Specifically, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction solution was filtered off as necessary, and then obtained in a poor solvent such as water, an aliphatic lower alcohol, or a mixed solution thereof. By adding the polymer component and precipitating the polymer component, it is precipitated as a solid, and by drying, a polyimide precursor or the like can be obtained. In order to improve the degree of purification, operations such as redissolution, reprecipitation and drying of the polyimide precursor may be repeated. Further, a step of removing ionic impurities using an ion exchange resin may be included.
• the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the resin composition. More preferably, it is more preferably 50% by mass or more. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass, based on the total solid content of the resin composition. % Or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less.
• the resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
• the resin composition of the present invention contains at least two kinds of resins.
• the resin composition of the present invention may contain two or more kinds of the specific resin and another resin described later in total, or may contain two or more kinds of the specific resin, but the specific resin may be contained. It is preferable to include two or more kinds.
• the resin composition of the present invention contains two or more kinds of specific resins, for example, two or more kinds of polyimides which are polyimide precursors and have different structures derived from dianhydride (R 115 in the above formula (2)). It is preferable to include a precursor.
• the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as “other resin”).
• Other resins include phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth) acrylic resin, (meth) acrylamide resin, urethane resin, butyral resin, styryl resin, polyether resin, polyester resin. And so on.
• a (meth) acrylic resin a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
• the molar amount of the polymerizable group contained in 1 g of the resin has a high polymerizable base value of 20,000 or less in weight average molecular weight. (1 ⁇ 10 -3 mol / g or more)
• the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved. can.
• the content of the other resin is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the resin composition. It is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more. More preferred. Further, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and more preferably 70% by mass, based on the total solid content of the resin composition. It is more preferably 0% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less.
• the content of the other resin may be low.
• the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less with respect to the total solid content of the resin composition. Is more preferable, 5% by mass or less is further preferable, and 1% by mass or less is even more preferable.
• the lower limit of the content is not particularly limited, and may be 0% by mass or more.
• the resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
• the resin composition of the present invention contains a compound A having a urea bond and no axis of symmetry as a radically polymerizable compound, and the compound A satisfies at least one of the following conditions 1 and 2.
• Condition 1 Compound A has two or more radically polymerizable groups.
• Condition 2 Compound A has at least one of a hydroxy group, an alkyleneoxy group, an amide group and a cyano group.
• Compound A is a compound having a structure that does not have an axis of symmetry.
• the fact that compound A does not have an axis of symmetry means that the compound does not have an axis that produces the same molecule as the original molecule by rotating the entire compound, and is a left-right asymmetric compound.
• the structural formula of compound A is described on paper, the fact that compound A does not have an axis of symmetry means that the structural formula of compound A cannot be expressed in a form having an axis of symmetry. It is considered that the aggregation of the compounds A is suppressed in the composition film because the compound A does not have an axis of symmetry.
• RN independently represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
• Compound A may contain two or more urea bonds, but an embodiment containing only one urea bond is also one of the preferred embodiments of the present invention.
• Compound A has a radically polymerizable group.
• a group having an ethylenically unsaturated bond is preferable.
• the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a maleimide group, and a (meth) acrylamide group. Examples thereof include (meth) acryloyloxy group, and (meth) acryloyloxy group is preferable.
• compound A has two or more radically polymerizable groups.
• the two or more radically polymerizable groups may have the same structure or different structures. Further, an embodiment in which the structures of the radically polymerizable groups contained in the compound A are all the same is also one of the preferred embodiments of the present invention.
• the number of radically polymerizable groups is preferably 2 to 10, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.
• the compound A contains a radically polymerizable group and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group and a cyano group.
• the number of radically polymerizable groups contained in compound A may be 1 or more, preferably 1 to 10, more preferably 1 to 4, and further preferably 1 to 3. It is preferably 1 or 2, and particularly preferably 1.
• RN is as described above.
• hydrocarbon group a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof is preferable.
• saturated aliphatic hydrocarbon group a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms is preferable, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is more preferable, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferable.
• Hydrocarbon groups are more preferred.
• an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, and two or more hydrogen atoms are removed from the benzene ring structure.
• Groups are more preferred.
• the other is directly bonded to a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof, and one of both ends of the urea bond is aromatic. It is more preferred that it binds directly to the hydrocarbon group and the other directly to the saturated aliphatic hydrocarbon group.
• the preferred carbon number of the saturated aliphatic hydrocarbon group or the aromatic hydrocarbon group is as described above.
• the compound A has at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group and a cyano group.
• the hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group, but is preferably an alcoholic hydroxy group.
• the alkyleneoxy group having 2 to 20 carbon atoms is preferable, the alkyleneoxy group having 2 to 10 carbon atoms is more preferable, and the alkyleneoxy group having 2 to 4 carbon atoms is more preferable.
• the alkyleneoxy group may be contained in the compound A as a polyalkyleneoxy group. In this case, the number of repetitions of the alkyleneoxy group is preferably 2 to 10, and more preferably 2 to 6.
• R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.
• Compound A has two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (however, a polyalkyleneoxy group when constituting a polyalkyleneoxy group), an amide group and a cyano group in the molecule.
• an embodiment having only one in the molecule is also one of the preferred embodiments of the present invention.
• the hydroxy group, the alkyleneoxy group, the amide group and the cyano group may be present at any position of the compound A, but from the viewpoint of chemical resistance, if the above condition 2 is satisfied, the compound A is the hydroxy.
• At least one selected from the group consisting of a group, an alkyleneoxy group, an amide group and a cyano group and at least one radically polymerizable group contained in the compound A are a linking group containing a urea bond (hereinafter, "linking group L2"). -1 ”) is also one of the preferred embodiments of the present invention.
• the compound A contains only one radically polymerizable group
• the radically polymerizable group contained in the compound A and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group and a cyano group are present.
• they are linked by a linking group containing a urea bond (hereinafter, also referred to as “linking radical L2-2”).
• linking radical L2-2 a linking group containing a urea bond
• the compound A contains an alkyleneoxy group (however, a polyalkyleneoxy group if it constitutes a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2, the alkyleneoxy group (However, the linking group L2-2).
• the structure of the polyalkyleneoxy group) bonded to the opposite side of the linking group L2-1 or the linking group L2-2 is not particularly limited, but is a hydrocarbon group or a radical.
• a polymerizable group or a group represented by a combination thereof is preferable.
• the preferred embodiment of the hydrocarbon group is the same as the preferred embodiment of the hydrocarbon group in the above-mentioned linking group L.
• the preferred embodiment of the radically polymerizable group is the same as the preferred embodiment of the radically polymerizable group in the above-mentioned compound A.
• the structure of the amide group is bonded to the opposite side of the linking group L2-1 or the linking group L2-2.
• a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof is preferable.
• the preferred embodiment of the hydrocarbon group is the same as the preferred embodiment of the hydrocarbon group in the above-mentioned linking group L.
• the preferred embodiment of the radically polymerizable group is the same as the preferred embodiment of the radically polymerizable group in the above-mentioned compound A.
• the carbon atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2, and the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2.
• Specific examples of the linking group L2-1 or L2-2 include the same group as the linking group L described above.
• * represents a bonding site with a radically polymerizable group, and when the structure shown as a specific example does not contain an alkyleneoxy group, # is selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group and a cyano group.
• the compound A preferably contains an aromatic group from the viewpoint of compatibility with the specific resin and the like.
• the aromatic group is preferably directly bonded to the urea bond contained in the compound A.
• the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and may have a structure in which these groups form a fused ring, but an aromatic hydrocarbon group is preferable.
• an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, and two or more hydrogen atoms are removed from the benzene ring structure.
• aromatic heterocyclic group a 5-membered ring or a 6-membered ring is preferable.
• aromatic heterocycle in such an aromatic heterocyclic group include pyrrol, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine and the like. .. These rings may be condensed with other rings such as indole and benzimidazole.
• hetero atom contained in the aromatic heterocyclic group a nitrogen atom, an oxygen atom or a sulfur atom is preferable.
• the aromatic group is, for example, at least one selected from the group consisting of the above-mentioned linking group L or the above-mentioned hydroxy group, alkyleneoxy group, amide group and cyano group, and at least one radical contained in the compound A. It is preferably contained in a linking group that links the polymerizable group.
• the number of atoms (linking chain length) between the urea bond and the radically polymerizable group in the compound A is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and 2 to 10. It is more preferable to have.
• compound A contains two or more urea bonds, two or more radically polymerizable groups, or two or more urea bonds and two or more radically polymerizable groups, the urea bonds and radically polymerizable groups Of the number of atoms (connected chain length) between them, the smallest one may be within the above range.
• the number of atoms (linking chain length) between a urea bond and a polymerizable group refers to the atomic chains on the path connecting between two atoms or a group of atoms to be linked.
• the one that connects the objects to be connected in the shortest time minimum number of atoms.
• the number of atoms (linkage chain length) between the urea bond and the radically polymerizable group (methacryloyloxy group) is 2.
• the compound A is preferably a compound represented by the following formula (1-1) or formula (1-2).
• RP1 and RP2 each independently represent a group containing at least one radically polymerizable group;
• RP1 represents a group containing at least one radically polymerizable group, and
• L3 represents a divalent linking group.
• the number of radically polymerizable groups in RP1 and RP2 is preferably 1 to 10, more preferably 1 to 4, and preferably 1 or 2, respectively. More preferred.
• the preferred embodiment of the radically polymerizable group in RP1 and RP2 is the same as the preferred embodiment of the radically polymerizable group in the above-mentioned compound A.
• RP1 and RP2 are independently represented by the following formula (RP-1).
• L RP1 represents a single bond or an m + 1 valent linking group
• X RP1 represents a radically polymerizable group
• m represents an integer of 1 or more
• * represents an integer of 1 or more. Represents the binding site with the urea bond.
• a group to which at least one group selected from the group is bonded is more preferable.
• RN is as described above.
• the structure adjacent to * which is a binding site with a urea bond, is preferably a hydrocarbon group.
• a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof is preferable, and a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms and carbon are preferable.
• An aromatic hydrocarbon group having 6 to 30 or a group represented by a combination thereof is more preferable, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a group obtained by removing 2 or more hydrogen atoms from the benzene ring. , Or a group represented by these bonds is more preferable.
• L RP1 is an alkylene group, an arylene group, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylene carbamate group, or 2 of these.
• the group combined as described above is preferable.
• the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.
• the arylene group is preferably an aromatic hydrocarbon group. Further, the arylene group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably a phenylene group.
• the carbon number of the alkylene group contained in the alkyleneoxy group, the alkyleneoxycarbonyl group, or the alkylenecarbamate group is preferably 2 to 20, and more preferably 2 to 10, respectively.
• m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1. ..
• the preferred embodiment of RP1 is the same as the preferred embodiment of RP1 in the formula (1-1).
• the molecular weight of compound A is preferably 100 to 2,000, preferably 150 to 1500, and more preferably 200 to 900.
• the compound A include, but are not limited to, the following compounds.
• the subscripts in parentheses represent the number of repetitions.
• the content of compound A with respect to the total solid content of the resin composition of the present invention is preferably 1 to 40% by mass.
• the lower limit is more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more.
• the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
• One compound A may be used alone, or two or more compounds may be mixed and used. When two or more kinds are used in combination, the total amount is preferably in the above range.
• the resin composition of the present invention further contains a polymerizable compound different from the above-mentioned compound A (hereinafter, also referred to as “another polymerizable compound”).
• the radically polymerizable compound further contains a compound different from the compound A (a radical cross-linking agent described later).
• the other polymerizable compound is a compound having a polymerizable group and does not correspond to the above-mentioned compound A.
• other polymerizable compounds include a compound having a radically polymerizable group but not a urea bond, a radically polymerizable group and a compound having a urea bond but having an axis of symmetry, and one radically polymerizable group. Includes compounds that have a urea bond but do not have any hydroxy, alkyleneoxy, amide or cyano groups.
• the other polymerizable compound include a radical cross-linking agent or another cross-linking agent, and it is preferable to include a radical cross-linking agent.
• the resin composition of the present invention preferably 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.
• Examples of 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, a (meth) acryloyl group, a maleimide group, and a (meth) acrylamide group.
• a (meth) acryloyl group As the group containing an ethylenically unsaturated bond, a (meth) acryloyl group, a (meth) acrylamide group and a vinylphenyl group are preferable, and from the viewpoint of reactivity, a (meth) acryloyl group is more preferable.
• the radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more ethylenically unsaturated bonds.
• the radical cross-linking agent may have three or more ethylenically unsaturated bonds.
• As the compound having two or more ethylenically unsaturated bonds a compound having 2 to 15 ethylenically unsaturated bonds is preferable, and a compound having 2 to 10 ethylenically unsaturated bonds is more preferable. The compound having is more preferable.
• the resin 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 group or an epoxy group, 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 polyelectron substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and a halogeno group.
• Substitution reaction products of unsaturated carboxylic acid esters or amides having a desorbing substituent such as or tosyloxy group with 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 are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
• Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acrylic acid, and mixtures thereof.
• 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.
• a preferable 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 groups and cardo resins can also be used.
• the compound described in JP-A No. 10-062986 together with specific examples as the formulas (1) and (2), which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, is also available. 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 (Nihonka) (Manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
• Dipentaerythritol penta (meth) acrylate commercially available KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)
• Dipenta Elythritol hexa (meth) acrylate commercially available KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
• these (meth) acryloyl groups are ethylene glycol residues or A structure bonded via
• SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
• SR-209 manufactured by Sartmer which is a bifunctional methacrylate having four ethyleneoxy chains.
• 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 are examples of the radical cross-linking agent.
• 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 (manufactured by Kayaku 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 Laid-Open No. 02-0322293, and Japanese Patent 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 compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, are 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.
• the radical cross-linking agent provided with the above 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 acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g.
• the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturable handling and further excellent in developability. Moreover, the polymerizability is good.
• the acid value is measured according to the description of JIS K 0070: 1992.
• the resin composition it is preferable to use bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
• Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate.
• the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula of about 200.
• 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 pattern (cured product).
• Examples of 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). ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
• N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglycidyl ether and the like are preferably used.
• the monofunctional radical cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
• the bifunctional or higher functional radical cross-linking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.
• 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 resin composition of the present invention.
• the lower limit is more preferably 5% by mass or more.
• the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
• the radical cross-linking agent may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably in the above range.
• the resin composition of the present invention contains another cross-linking agent different from the above-mentioned radical cross-linking agent.
• the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and is exposed to a photoacid generator, a photobase generator, or the like to generate another compound in the composition or a reaction thereof.
• a compound having a plurality of groups in the molecule that promotes a reaction to form a covalent bond with a substance is preferable, and a covalent bond is formed with another compound in the composition or a reaction product thereof.
• a compound having a plurality of groups in the molecule in which the reaction to be carried out is promoted by the action of an acid or a base is preferable.
• the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
• a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group is preferable, and the compound is selected from the group consisting of an acyloxymethyl group, a methylol group and an alkoxymethyl group.
• a compound having a structure in which at least one of the above groups is directly bonded to a nitrogen atom is 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 changed to an acyloxymethyl group, a methylol group, or a methylol group.
• examples thereof include compounds having a structure substituted with an alkoxymethyl group.
• the method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
• the cross-linking agent using melamine is a melamine-based cross-linking agent
• the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent
• the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent.
• a cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
• the resin 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 is preferably a glycoluril-based cross-linking agent and a melamine-based cross-linking agent described later. It is more preferred to include at least one compound selected from the group consisting of agents.
• the alkoxymethyl group or the acyloxymethyl group is directly substituted on the aromatic group or the nitrogen atom of the following urea structure, or on triazine.
• the alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
• the total number of alkoxymethyl groups and acyloxymethyl groups contained in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
• the molecular weight of the compound is preferably 1500 or less, preferably 180 to 1200.
• R 100 represents an alkyl group or an acyl group.
• R 101 and R 102 each independently represent a monovalent organic group and may be bonded to each other to form a ring.
• Examples of the compound in which the alkoxymethyl group or the acyloxymethyl group is directly substituted with the aromatic group include compounds as shown in the following general formula.
• X represents a single-bonded or divalent organic group
• each R 104 independently represents an alkyl group or an acyl group
• R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
• R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
• R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
• R 103 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group.
• R 4 represents a group that decomposes by the action of an acid to produce an alkali-soluble group
• It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• R5 represents a group desorbed by the action
• R 105 independently represents an alkyl group or an alkenyl group, a, b and c are independently 1 to 3, d is 0 to 4, e is 0 to 3, and f is 0 to 3. A + d is 5 or less, b + e is 4 or less, and c + f is 4 or less.
• R 5 in a group that decomposes by the action of an acid to produce an alkali-soluble group a group that is eliminated by the action of an acid, and a group represented by -C (R 4 ) 2 COOR 5 , for example, -C (R 36 ).
• R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
• R 36 and R 37 may be coupled to each other to form a ring.
• an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
• the alkyl group may be linear or branched.
• cycloalkyl group a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
• the cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring.
• the aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
• aralkyl group an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
• the above-mentioned aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those of the above-mentioned preferred embodiments of alkyl and aryl groups.
• the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Further, these groups may further have a known substituent as long as the effect of the present invention can be obtained.
• R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
• the group that decomposes by the action of an acid to produce an alkali-soluble group, or the group that is desorbed by the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or the like. More preferably, it is a tertiary alkyl ester group or an acetal group.
• Examples of the compound having an alkoxymethyl group include the following structures.
• Examples of the compound having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compound is changed to an acyloxymethyl group.
• Examples of the compound having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
• the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group a commercially available compound may be used, or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.
• melamine-based cross-linking agent examples include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine 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.
• Uril trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monoethoxymethylated glycol uryl, diethoxymethylated glycol uryl, triethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl , Dipropoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol
• Glycoluril-based cross-linking agents such as uryl; Urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea,
• benzoguanamine-based cross-linking agent examples include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
• Tetramethoxymethylated benzoguanamine Tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetra Examples thereof include propoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like.
• 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).
• Compounds to which the group of the species is directly bonded are 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, and DML-OEP.
• the resin composition of the present invention contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.
• 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 resin composition of the present invention.
• 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.
• Examples include, but are not limited to, contained silicones.
• n is an integer of 1 to 5
• m is an integer of 1 to 20.
• n is preferably 1 to 2 and m is preferably 3 to 7 from the viewpoint of achieving both heat resistance and improvement in elongation.
• oxetane compound compound having an oxetanyl group
• the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, and the like.
• examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like.
• Aron Oxetane series (for example, OXT-121, OXT-221) manufactured by Toagosei Co., Ltd. can be preferably used, and these can be used alone or in combination of two or more. good.
• benzoxazine compound examples include Pd-type benzoxazine, Fa-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), a benzoxazine adduct of a polyhydroxystyrene resin, and a phenol novolac-type dihydrobenzo.
• examples include oxazine compounds. These may be used alone or in combination of two or more.
• the content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and 0. It is more preferably 5 to 15% by mass, and particularly preferably 1.0 to 10% by mass.
• the other cross-linking agent may be contained in only one kind, or may be contained in two or more kinds. When two or more other cross-linking agents are contained, the total is preferably in the above range.
• the resin composition of the present invention contains a radical polymerization initiator.
• the radical polymerization initiator is preferably a radical polymerization initiator that can initiate polymerization by light and / or heat.
• the photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators.
• a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable.
• it may be an active agent that causes some action with a photoexcited sensitizer and generates an active radical.
• the photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol -1 ⁇ cm -1 within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). Is 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).
• a known compound can be arbitrarily used.
• halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
• acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives and the like.
• a metallocene compound an organic boron compound
• 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 JP-A-2015-087611 is exemplified, and the content thereof is incorporated in the present specification.
• Kayacure-DETX-S 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 be preferably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and the contents thereof are described in the present specification. Be incorporated.
• Examples of the ⁇ -hydroxyketone initiator include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, and DAROCUR 1173.
• Omnirad 184 Omnirad 1173
• Omnirad 2959 Omnirad 127
• IRGACURE 184 IRGACURE is a registered trademark
• DAROCUR 1173 DAROCUR 1173
• DAROCUR 1173 DAROCUR 1173.
• -2959, IRGACURE 127 (trade name: both manufactured by BASF) can be used.
• Omnirad 907 As the ⁇ -aminoketone-based initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 369, all of which are IRGACURE 37. (Manufactured by the company) can be used.
• the aminoacetophenone-based initiator 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, and the contents thereof are incorporated in the present specification.
• acylphosphine oxide-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
• Omnirad 819, Omnirad TPO (all manufactured by IGM Resins BV), IRGACURE-819 and IRGACURE-TPO (trade name: all manufactured by BASF) can be used.
• metallocene compound examples include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF), Keycure VIS 813 (manufactured by King Brother Chem), and the like.
• the photoradical polymerization initiator is more preferably an oxime compound.
• the oxime compound By using the oxime compound, it becomes possible to improve the exposure latitude more effectively.
• the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
• oxime compound examples include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, the compound described in JP-A-2006-342166, and J. Am. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385. Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-109766, compounds described in Japanese Patent No.
• Preferred oxime compounds include, for example, compounds having the following structures, 3- (benzoyloxy (imino)) butane-2-one, 3- (acetoxy (imino)) butane-2-one, 3- (propionyloxy (propionyloxy).
• IRGACURE OXE 01 IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PTOMER N-1919 (manufactured by ADEKA Corporation, JP-A-2012-014052).
• a radical polymerization initiator 2) is also preferably used.
• TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-730, NCI-831 and ADEKA ARCULDS NCI-930 (manufactured by ADEKA Corporation) are also used. be able to.
• DFI-091 manufactured by Daito Chemix Co., Ltd.
• SpeedCure PDO manufactured by SARTOMER ARCEMA
• an oxime compound having the following structure can also be used.
• an oxime compound having a fluorene ring can also be used.
• Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 6636081, the contents of which are incorporated in the present specification.
• an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
• Specific examples of such oxime compounds include the compounds described in WO 2013/083505, the contents of which are incorporated herein.
• an oxime compound having a fluorine atom It is also possible to use an oxime compound having a fluorine atom.
• an oxime compound include the compounds described in JP-A-2010-262028, the compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013.
• the compound (C-3) and the like described in paragraph 0101 of the publication No. 164471 are mentioned, and the contents thereof are incorporated in the present specification.
• an oxime compound having a nitro group can be used as the photopolymerization initiator.
• the oxime compound having a nitro group is also preferably a dimer.
• Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466. Examples of the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 are incorporated herein by reference. Further, examples of the oxime compound having a nitro group include ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation).
• an oxime compound having a benzofuran skeleton can also be used.
• Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
• an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
• Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055, and the contents thereof are incorporated in the present specification.
• an oxime compound having an aromatic ring group Ar OX1 having an electron-attracting group introduced into the aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used.
• the electron-attracting group of the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group and a cyano group.
• the benzoyl group may have a substituent.
• the substituent include a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group and an arylsulfanyl group.
• an acyl group or an amino group more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group, and more preferably an alkoxy group or an alkyl group. It is more preferably a sulfanyl group or an amino group.
• the oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). preferable.
• RX1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group.
• RX2 contains an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group and an aryl.
• RX3 to RX14 independently represent a hydrogen atom or a substituent. However, at least one of RX10 to RX14 is an electron-withdrawing group.
• RX12 is an electron-withdrawing group and RX10 , RX11 , RX13 and RX14 are hydrogen atoms.
• oxime compound OX examples include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated in the present specification.
• the most preferable oxime compound includes 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. Incorporated herein.
• the photoradical polymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triaryl.
• Compounds are preferred.
• More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds.
• At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable. ..
• the photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone).
• 2-benzyl such as benzophenone
• -2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-aromatic ketones such as morpholino-propanone-1, alkylanthraquinone, etc.
• benzoin ether compounds such as benzoin alkyl ether
• benzoin compounds such as benzoin and alkyl benzoin
• benzyl derivatives such as benzyl dimethyl ketal.
• a compound represented by the following formula (I) can also be used.
• 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.
• RI01 is a group represented by the formula (II). It is the same group as RI00 , and RI02 to RI04 are independently alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogen atoms.
• R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
• the photoradical polymerization initiator the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used, and the contents thereof are incorporated in the present specification.
• a bifunctional or trifunctional or higher photoradical polymerization initiator may be used as the photoradical polymerization initiator.
• two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained.
• the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the resin composition with time can be improved.
• Specific examples of the bifunctional or trifunctional or higher functional photo-radical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No.
• the content of the radical polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably, with respect to the total solid content of the resin composition of the present invention. It is 0.5 to 15% by mass, more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total amount is preferably in the above range. Since the photopolymerization initiator may also function as a thermal polymerization initiator, cross-linking with the photopolymerization initiator may be further promoted by heating an oven, a hot plate, or the like.
• the resin composition may contain a sensitizer.
• the sensitizer absorbs specific active radiation and becomes an electronically excited state.
• the sensitizer in the electron-excited state comes into contact with the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur.
• the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid or a base.
• Usable sensitizers include benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthracinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazole triazole azo.
• Pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, penzopyran, indigo and the like can be used.
• sensitizer examples include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal).
• the content of the sensitizer is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. It is more preferably present, and even more preferably 0.5 to 10% by mass.
• the sensitizer may be used alone or in combination of two or more.
• the resin composition of the present invention may contain a chain transfer agent.
• Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684.
• Examples of the chain transfer agent include RAFT (Reversible Addition Fragmentation chain Transfer), which is a group of compounds having -S-S-, -SO2 -S-, -NO-, SH, PH, SiH, and GeH in the molecule.
• Dithiobenzoate, trithiocarbonate, dithiocarbamate, xantate compound and the like having a thiocarbonylthio group used for polymerization are used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
• thiol compounds can be preferably used.
• the content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the resin composition of the present invention. 1 to 10 parts by mass is more preferable, and 0.5 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.
• the resin composition of the present invention may contain a base generator.
• the base generator is a compound capable of generating a base by a physical or chemical action.
• Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
• the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator.
• the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product become good. The performance as an interlayer insulating film for a wiring layer is improved.
• the base generator may be an ionic base generator or a nonionic base generator.
• Examples of the base generated from the base generator include secondary amines and tertiary amines.
• the base generator according to the present invention is not particularly limited, and a known base generator can be used.
• Known base generators include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetoamide compounds, carbamates compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimides.
• Compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, ⁇ -lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds and the like can be used.
• Specific examples of the compound of the nonionic base generator include a compound represented by the formula (B1), the formula (B2), or the formula (B3).
• Rb 1 , Rb 2 and Rb 3 are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. Further, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group.
• the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.
• Rb 1 , Rb 2 and Rb 3 contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure.
• the cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable.
• the single ring is preferably a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring.
• a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.
• Rb 1 and Rb 2 are hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and alkenyl groups (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ⁇ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have a substituent as long as the effect of the present invention is exhibited. Rb 1 and Rb 2 may be bonded to each other to form a ring.
• Rb 1 and Rb 2 are particularly linear, branched, or cyclic alkyl groups which may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
• substituents preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms.
• It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
• cyclohexyl groups are more preferred.
• an alkyl group preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms
• an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6.
• alkenyl groups preferably 2 to 24 carbon atoms, more preferably 2 to 12
• arylalkyl groups preferably 7 to 23 carbon atoms, 7 to 19 are more preferred.
• 7 to 12 is more preferable), an arylalkenyl group (preferably 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms), and an alkoxyl group (preferably 1 to 24 carbon atoms, 2 to 2 to 24).
• 18 is more preferred, 3 to 12 are more preferred), aryloxy groups (6 to 22 carbons are preferred, 6 to 18 are more preferred, 6 to 12 are even more preferred), or arylalkyloxy groups (7 to 12 carbons).
• 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable).
• a cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable.
• Rb 3 may further have a substituent as long as the effect of the present invention is exhibited.
• the compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
• Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively.
• Rb 13 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effect of the present invention is exhibited.
• Rb 13 is preferably an arylalkyl group.
• Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
• Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
• 2 to 8 are more preferable, 2 to 3 are more preferable
• aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable
• 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is even more preferable), and a hydrogen atom is preferable.
• Rb 35 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). , 7-12 is more preferable), and an aryl group is preferable.
• the compound represented by the formula (B1-1) is also preferable.
• Rb 11 and Rb 12 are synonymous with Rb 11 and Rb 12 in the formula (B1-1).
• Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7).
• Rb 17 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
• L is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the connecting chain connecting the adjacent oxygen atom and the carbon atom, and the number of atoms on the path of the connecting chain is Represents a hydrocarbon group of 3 or more.
• RN1 and RN2 each independently represent a monovalent organic group.
• linking chain refers to an atomic chain on a path connecting two atoms or a group of atoms to be linked, which is connected at the shortest (minimum number of atoms).
• L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group, and the linking chain is composed of four carbon atoms, and is on the path of the linking chain. (That is, the number of atoms constituting the connecting chain, hereinafter also referred to as "linking chain length" or "connecting chain length”) is 4.
• the number of carbon atoms in L in the formula (B3) is preferably 3 to 24.
• the upper limit is more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less.
• the lower limit is more preferably 4 or more.
• the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and 5 The following is particularly preferable.
• the chain length of L is preferably 4 or 5, and most preferably 4.
• Specific preferred compounds of the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/06614 and the compounds described in paragraph numbers 0143 to 0177 of International Publication No. 2018/038002. Can be mentioned.
• the base generator contains a compound represented by the following formula (N1).
• RN1 and RN2 each independently represent a monovalent organic group
• RC1 represents a hydrogen atom or a protecting group
• L represents a divalent linking group
• L is a divalent linking group, preferably a divalent organic group.
• the linking chain length of the linking group is preferably 1 or more, and more preferably 2 or more.
• the upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less.
• the linking chain length is the number of atoms present in the atomic arrangement that is the shortest route between the two carbonyl groups in the equation.
• RN1 and RN2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and a hydrocarbon group (preferably 3 to 12 carbon atoms). It is preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms), and specifically, an aliphatic hydrocarbon group (preferably 1 to 12 carbon atoms). Is more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and an aliphatic hydrocarbon can be mentioned. Groups are preferred.
• an aliphatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are contained in the aliphatic hydrocarbon chain or the aromatic ring. It may have an oxygen atom in the substituent.
• an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.
• a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a chain alkyl group and a cyclic alkyl group, and an oxygen atom are contained in the chain.
• Examples thereof include alkyl groups having.
• the linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms.
• the linear or branched chain alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, or an isopropyl group.
• Examples thereof include a group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group.
• the cyclic alkyl group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.
• the group related to the combination of the chain alkyl group and the cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms.
• Examples of the group related to the combination of the chain alkyl group and the cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, an ethylcyclohexylethyl group and the like.
• the alkyl group having an oxygen atom in the chain is preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms.
• the alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. Among them, alkyl groups having 5 to 12 carbon atoms are preferable for RN1 and RN2 from the viewpoint of increasing the boiling point of the decomposition-generated base described later.
• a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
• RN1 and RN2 may be connected to each other to form an annular structure.
• oxygen atoms or the like may be contained in the chain.
• the cyclic structure formed by RN1 and RN2 may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferable.
• a 5-membered ring or a 6-membered ring containing a nitrogen atom in the formula (N1) is preferable, and for example, a pyrrol ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, and the like.
• Pyrazolidine ring, piperidine ring, piperazine ring, morpholine ring and the like are mentioned, and pyrroline ring, pyrrolidine ring, piperidine ring, piperazine ring, morpholine ring and the like are preferable.
• RC1 represents a hydrogen atom or a protecting group, and a hydrogen atom is preferable.
• the protecting group a protecting group that decomposes by the action of an acid or a base is preferable, and a protecting group that decomposes by an acid is preferable.
• the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain.
• the chain or cyclic alkyl group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group and the like.
• Specific examples of the chain-like alkyl group having an oxygen atom in the chain include an alkyloxyalkyl group, and more specifically, a methyloxymethyl (MOM) group, an ethyloxyethyl (EE) group and the like. Can be mentioned.
• Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyranyl (THP) group and the like.
• the divalent linking group constituting L is not particularly specified, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable.
• the hydrocarbon group may have a substituent, or may have an atom of a type other than a carbon atom in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain. More preferably, a divalent aromatic hydrocarbon group or a group relating to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group is preferable.
• a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferable. It is preferable that these groups do not have an oxygen atom.
• the divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms.
• the divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
• the divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
• the group (for example, an arylene alkyl group) relating to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and 7 to 18 carbon atoms. 10 is more preferable.
• linking group L examples include a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, and an alkylene group having an oxygen atom in the chain.
• a linear or branched chain alkaneylene group, a cyclic alkaneylene group, an arylene group, or an arylene alkylene group is preferable.
• the linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
• the cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
• the group related to the combination of the chain alkylene group and the cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
• the alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched.
• the alkylene group having an oxygen atom in the chain is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms.
• the linear or branched chain-like alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms.
• the cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
• the arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
• the arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
• a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propandiyl group (particularly 1, 3-Propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cisvinylene group), phenylene group (1,2-phenylene group), phenylene methylene group (especially 1,2-phenylene) Methylene group) and ethyleneoxyethylene group (particularly 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.
• Examples of the base generator include the following, but the present invention is not construed as being limited thereto.
• the molecular weight of the non-ionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
• the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
• Specific preferable compounds of the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.
• ammonium salt examples include, but are not limited to, the following compounds.
• iminium salt examples include, but are not limited to, the following compounds.
• the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention.
• the lower limit is more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more.
• the upper limit is more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, 5 parts by mass or less, or 4 parts by mass or less.
• the base generator one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
• the resin composition of the present invention preferably contains a solvent.
• a solvent a known solvent can be arbitrarily used.
• the solvent is preferably an organic solvent.
• the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas and alcohols.
• esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
• alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) (Ethyl ethoxyacetate, etc.)
• 3-alkyloxypropionic acid alkyl esters eg, methyl 3-alkyloxypropionic acid, ethyl 3-alkyloxypropionic acid, etc.) (eg, methyl 3-methoxypropionic acid, 3-methoxypropionic acid, etc.) (Ethyl, methyl 3-ethoxypropionic acid, ethyl 3-ethoxypropionic acid, etc.)
• 2-alkyloxypropionic acid alkyl esters eg, methyl 2-alkyloxypropionic acid alkyl esters
• Suitable examples include ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutate, ethyl hexanoate, ethyl heptanate, dimethyl malonate, diethyl malonate and the like. ..
• ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.
• ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.
• cyclic hydrocarbons for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.
• sulfoxides for example, dimethyl sulfoxide is preferable.
• N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferable.
• Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
• the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
• the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass.
• the solvent content may be adjusted according to the desired thickness of the coating film and the coating method.
• the resin composition of the present invention may contain only one type of solvent, or may contain two or more types of solvent. When two or more kinds of solvents are contained, the total is preferably in the above range.
• the resin 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 adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesive aid, a titanium-based adhesive aid, a compound having a sulfonamide structure and a compound having a thiourea structure, a phosphoric acid derivative compound, and a ⁇ -ketoester. Examples thereof include compounds and amino compounds.
• silane coupling agent examples include the compound described in paragraph 0167 of International Publication No. 2015/199219, the compound described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraph of International Publication No. 2011/080992.
• examples thereof include the compounds described in paragraph 0055 and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein by reference.
• silane coupling agents examples include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycid.
• Aluminum-based adhesive aid examples include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), ethyl acetoacetate aluminum diisopropylate, and the like.
• the content of the metal adhesive improving agent is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and further preferably 0. It is in the range of 5 to 5 parts by mass.
• the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more kinds are used, it is preferable that the total is in the above range.
• the resin 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 membrane.
• the migration inhibitor is not particularly limited, but has a heterocyclic ring (pyran ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
• triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole-based compounds such as phenyltetrazole and 5-amino-1H-tetrazole 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 the rust preventive agent described in paragraph 0094 of JP2013-015701, the compound described in paragraphs 0073 to 0076 of JP2009-283711, and JP-A-2011-059656.
• 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 content is incorporated herein.
• 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 resin composition of the present invention. , 0.05 to 2.0% by mass, more preferably 0.1 to 1.0% by mass.
• the migration inhibitor may be only one kind or two or more kinds. When there are two or more types of migration inhibitors, the total is preferably in the above range.
• the resin composition of the present invention preferably contains a polymerization inhibitor.
• the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl-free radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, and metal compounds.
• Specific compounds of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, 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-nitrosophenyl Hydroxyamine primary cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2, 6-Di-tert-butyl-4-methylphenol
• polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used, and the contents thereof are described in the present specification. Be incorporated.
• the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, preferably 0 to 20% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.
• the polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
• the resin composition of the present invention comprises various additives such as a surfactant, a higher fatty acid derivative, a thermal polymerization initiator, an inorganic particle, and an ultraviolet absorber, if necessary, as long as the effects of the present invention can be obtained.
• Organic titanium compounds, antioxidants, antiaggregating agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries eg, antifoaming agents, flame retardant agents, etc.
• properties such as film physical characteristics can be adjusted.
• the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
• surfactant various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used.
• the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
• the liquid characteristics (particularly, fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property are further improved.
• the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved.
• the applicability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.
• fluorine-based surfactant examples include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479.
• F482, F554, F780, RS-72-K above, manufactured by DIC Co., Ltd.
• Florard FC430, FC431, FC171, Novek FC4430, FC4432 aboveve, manufactured by 3M Japan Ltd.
• the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and the compounds described in paragraphs 0117 to 0132 of JP-A-2011-132503 can also be used. Incorporated herein.
• a block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090, the contents of which are incorporated in the present specification.
• the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
• a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
• the weight average molecular weight of the above compounds is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
• a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, the contents of which are incorporated in the present specification. Examples of commercially available products include Megafuck RS-101, RS-102, and RS-718K manufactured by DIC Corporation.
• the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
• a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, and has good solubility in the composition.
• silicone-based surfactant examples include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF6001, KF6002 (all manufactured by Shinetsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (all manufactured by Big Chemie Co., Ltd.) and the like.
• hydrocarbon-based surfactant examples include Pionin A-76, New Calgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, and Pionin.
• Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylates, glycerol ethoxylates, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. Examples thereof include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
• organosiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.
• (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 77, No. 90, No. Examples include 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).
• anion-type surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.
• the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
• the resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and the resin composition of the present invention is dried in the process of drying after application. It may be unevenly distributed on the surface of.
• the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the resin composition of the present invention.
• 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 resin composition of the present invention may contain a thermal polymerization initiator, and may particularly contain a thermal radical polymerization initiator.
• the thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. Since the polymerization reaction of the resin and the polymerizable compound can be promoted by adding the thermal radical polymerization initiator, the solvent resistance can be further improved. Further, the above-mentioned photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
• thermal radical polymerization initiator examples include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated in the present specification.
• 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 resin composition of the present invention. , More preferably 0.5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.
• the resin composition of the present invention may contain inorganic particles.
• specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
• the average particle size of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, further preferably 0.03 to 1.0 ⁇ m, and 0.04 to 0.5 ⁇ m. Especially preferable.
• the average particle size of the fine particles is a primary particle size and a volume average particle size.
• the volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can be measured by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction / scattering method.
• the composition of the present invention may contain an ultraviolet absorber.
• an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
• salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like, and examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-.
• Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxyl-4-octoxybenzophenone and the like can be mentioned.
• benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3).
• Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like.
• the triazine-based ultraviolet absorber 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) )-1,3,5-Triazine, 2- [4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin
• the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.
• the composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.
• the resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.
• Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
• Specific examples of the organic titanium compound are shown in I) to VII) below:
• I) Titanium chelate compound Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the resin composition has good storage stability and a good curing pattern can be obtained.
• Specific examples are titanium bis (triethanolamine) diisopropoxiside, titanium di (n-butoxide) bis (2,4-pentanegenate, titanium diisopropoxiside bis (2,4-pentanegeonate)).
• Titanium Alkoxy Titanium Compounds For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis ⁇ 2,2- (Aryloxymethyl) Butokiside ⁇ ] etc.
• Titanocene compounds for example, pentamethylcyclopentadienyl titanium trimethoxide, bis ( ⁇ 5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis ( ⁇ 5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
• Monoalkoxytitanium compound For example, titaniumtris (dioctylphosphate) isopropoxyside, titaniumtris (dodecylbenzenesulfonate) isopropoxyside and the like.
• Titanium oxide compound For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
• the organic titanium compound at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound has better chemical resistance. It is preferable from the viewpoint of playing.
• -Pyrrole-1-yl) phenyl) titanium is preferred.
• the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the specific resin.
• the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are more effectively exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition Excellent.
• the composition of the present invention may contain an antioxidant.
• an antioxidant By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material.
• the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like.
• the phenol compound any phenol compound known as a phenolic antioxidant can be used.
• Preferred phenolic compounds include hindered phenolic compounds.
• a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable.
• a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
• a compound having a phenol group and a phosphite ester group in the same molecule is also preferable.
• a phosphorus-based antioxidant can also be preferably used.
• antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, and Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like.
• the antioxidant the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, and the contents thereof are incorporated in the present specification.
• the composition of the present invention may contain a latent antioxidant, if necessary.
• the latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant.
• Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219, the contents of which are incorporated in the present specification.
• Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation).
• preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).
• R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R 6 represents an alkylene having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). Represents a group.
• R 7 represents a 1- to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom.
• k represents an integer of 1 to 4.
• the compound represented by the formula (3) suppresses the oxidative deterioration of the aliphatic group and the phenolic hydroxyl group of the resin.
• metal oxidation can be suppressed by the rust preventive action on the metal material.
• k is more preferably an integer of 2 to 4.
• R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-.
• R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-.
• Examples thereof include O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent.
• alkyl ether group and -NH- from the viewpoint of solubility in a developing solution and metal adhesion
• -NH- is preferable from the viewpoint of interaction with a resin and metal adhesion due to metal complex formation. More preferred.
• Examples of the compound represented by the general formula (3) include the following, but the compound is not limited to the following structure.
• the amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to the resin.
• the addition amount is 0.1 part by mass or more, the effect of improving the elongation property and the adhesion to the metal material can be easily obtained even in a high temperature and high humidity environment, and when the addition amount is 10 parts by mass or less, for example, the emulsion is exposed.
• the interaction with the agent improves the sensitivity of the resin composition.
• Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
• the resin composition of the present embodiment may contain an anti-aggregation agent, if necessary.
• the anti-aggregation agent include sodium polyacrylate and the like.
• one type of anti-aggregation agent may be used alone, or two or more types may be used in combination.
• the composition of the present invention may or may not contain an anti-aggregation agent, but when it is contained, the content of the anti-aggregation agent is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less.
• the resin composition of the present embodiment may contain a phenolic compound, if necessary.
• phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, and BisP-CP.
• one type of phenolic compound may be used alone, or two or more types may be used in combination.
• the composition of the present invention may or may not contain a phenolic compound, but when it is contained, the content of the phenolic compound is 0.01% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 30% by mass or more, and more preferably 0.02% by mass or more and 20% by mass or less.
• Examples of other polymer compounds include siloxane resins, (meth) acrylic polymers copolymerized with (meth) acrylic acids, novolak resins, resole resins, polyhydroxystyrene resins and copolymers thereof.
• the other polymer compound may be a modified product into which a cross-linking group such as a methylol group, an alkoxymethyl group, or an epoxy group is introduced.
• one type of other polymer compound may be used alone, or two or more types may be used in combination.
• the composition of the present invention may or may not contain other polymer compounds, but when it is contained, the content of the other polymer compounds is 0 with respect to the total solid content mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.
• the viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm 2 / s to 12,000 mm 2 / s is preferable, 2,000 mm 2 / s to 10,000 mm 2 / s is more preferable, and 2,500 mm 2 / s to 8,000 mm. 2 / s is more preferable. Within the above range, it becomes easy to obtain a highly uniform coating film.
• the water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.
• the metal content of the resin composition of the present invention is preferably less than 5 parts by mass (parts per million), more preferably less than 1 part by mass, still more preferably less than 0.5 parts by mass, from the viewpoint of insulating properties.
• the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel and the like, but metals contained as a complex of an organic compound and a metal are excluded. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.
• the resin composition of the present invention selects a raw material having a low metal content as the raw material constituting the resin composition of the present invention.
• examples thereof include a method of filtering the raw materials constituting the product by a filter, a method of lining the inside of the device with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible.
• the resin 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 less than 200 mass ppm from the viewpoint of wiring corrosiveness. Is more preferable. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
• the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
• ion exchange treatment and the like are preferably mentioned.
• a conventionally known storage container can be used as the storage container for the resin composition of the present invention.
• a multi-layer bottle having a container inner wall made of 6 types and 6 layers of resin and 6 types of resin are used as the storage container. 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 cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
• the curing of the resin composition is preferably by heating, more preferably the heating temperature is in the range of 120 ° C to 400 ° C, further preferably in the range of 140 ° C to 380 ° C, and 170 ° C. It is particularly preferable that the temperature is in the range of about 350 ° C.
• the form of the cured product of the resin composition is not particularly limited, and can be selected according to the intended use, such as a film shape, a rod shape, a spherical shape, and a pellet shape.
• the cured product is preferably in the form of a film.
• this cured product can be used for forming a protective film on the wall surface, forming via holes for conduction, adjusting impedance, capacitance or internal stress, and imparting a heat dissipation function. You can also choose the shape.
• the film thickness of this cured product (film made of the cured product) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
• the shrinkage rate of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less.
• the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more. If it is 70% or more, it may be a cured product having excellent mechanical properties.
• the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more.
• the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180 ° C. or higher, more preferably 210 ° C. or higher, and even more preferably 230 ° C. or higher.
• the resin composition of the present invention can be prepared by mixing each of the above components.
• the mixing method is not particularly limited, and a conventionally known method can be used. For mixing, mixing with a stirring blade, mixing with a ball mill, mixing by rotating the tank itself, or the like can be adopted.
• the temperature during mixing is preferably 10 to 30 ° C, more preferably 15 to 25 ° C.
• the filter hole diameter may be, for example, 5 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, still more preferably 0.1 ⁇ m or less.
• the filter material is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferable to use HDPE (high density polyethylene).
• the filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel for use.
• filters having different pore diameters or materials may be used in combination.
• the connection mode include a mode in which an HDPE filter having a hole diameter of 1 ⁇ m is connected in series as the first stage and an HDPE filter having a hole diameter of 0.2 ⁇ m is connected in series as the second stage.
• various materials may be filtered a plurality of times. When filtering multiple times, circulation filtration may be used. Moreover, you may pressurize and perform filtration.
• the pressure to be pressurized is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. , 0.05 MPa or more and 0.5 MPa or less is more preferable.
• impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
• the 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 resin composition filled in the bottle may be placed under reduced pressure to perform a step of degassing.
• the method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film. Further, in the method for producing a cured product of the present invention, the film forming step, the exposure step of selectively exposing the film formed by the film forming step, and the film exposed by the exposure step are developed using a developing solution. It is more preferable to include a developing step of forming a pattern.
• the method for producing a cured product of the present invention includes the film forming step, the exposure step, the developing step, and the heating step for heating the pattern obtained by the developing step and the post-development for exposing the pattern obtained by the developing step.
• the production method of the present invention includes the above-mentioned film forming step and the above-mentioned step of heating the film.
• the production method of the present invention includes the above-mentioned film forming step and the above-mentioned step of heating the film.
• the resin composition of the present invention can be applied to a substrate to form a film and can be used in a film forming step.
• the method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition onto a substrate to form a film.
• the type of the 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, vapor-deposited film, etc.
• semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, vapor-deposited film, etc.
• a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe for example, a substrate formed of metal, or a substrate in which a metal layer is formed by, for example, plating or vapor deposition, etc.
• SOG Spin On Glass
• TFT thin film array base material
• mold base material mold base material
• electrode plate of plasma display panel (PDP) and the like, and are not particularly limited.
• a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a molded base material are more preferable. Further, these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface thereof.
• the shape of the base material is not particularly limited, and may be circular or rectangular. The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.
• a plate-shaped base material (substrate), preferably a panel-shaped base material (board) is used as the base material.
• a resin composition when a resin composition is applied to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer to form a film, the resin layer or the metal layer becomes a base material.
• Coating is preferable as a means for applying the resin composition of the present invention on a substrate.
• the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method.
• An inkjet method and the like are exemplified. From the viewpoint of film thickness uniformity, a spin coating method, a slit coating method, a spray coating method, or an inkjet method is more preferable, and spin coating is performed from the viewpoint of film thickness uniformity and productivity.
• the method and the slit coating method are preferable. By adjusting the solid content concentration and the coating conditions of the resin composition according to the method, a film having a desired thickness can be obtained.
• 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 3,500 rpm for about 10 seconds to 3 minutes. Further, it is also possible to apply a method of transferring a coating film previously applied onto a temporary support by the above-mentioned application method onto a substrate.
• the production method described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0090 to 0108 of JP-A-2006-047592 can be suitably used in the present invention.
• a step of removing the excess film at the end of the base material may be performed. Examples of such a process include edge bead rinse (EBR), back rinse and the like.
• EBR edge bead rinse
• a pre-wet step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.
• the film may be subjected to a step (drying step) of drying the film (layer) formed to remove the solvent after the film forming step (layer forming step). That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step. Further, it is preferable that the drying step is performed after the film forming step and before the exposure step.
• the drying temperature of the film in the drying step is preferably 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. Further, drying may be performed by reducing the pressure.
• the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, more preferably 2 minutes to 7 minutes.
• the film may be subjected to an exposure step of selectively exposing the film. That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed by the film forming step. Selective exposure means exposing a part of the film. Further, by selectively exposing the film, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.
• the exposure amount is not particularly determined as long as the resin composition of the present invention can be cured, but for example, it is preferably 50 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ / cm 2 . Is more preferable.
• the exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
• the exposure wavelengths are as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength). 436 nm), h-ray (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm).
• the resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays. As a result, particularly high exposure sensitivity can be obtained.
• the exposure method is not particularly limited as long as it is a method in which at least a part of the film made of the resin composition of the present invention is exposed, but exposure using a photomask, exposure by a laser direct imaging method, or the like is possible. Can be mentioned.
• the film may be subjected to a step of heating after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.
• the post-exposure heating step can be performed after the exposure step and before the developing step.
• the heating temperature in the post-exposure heating step is preferably 50 ° C to 140 ° C, more preferably 60 ° C to 120 ° C.
• the heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
• the heating rate in the post-exposure heating step is preferably 1 to 12 ° C./min, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min from the temperature at the start of heating to the maximum heating temperature. Further, the heating rate may be appropriately changed during heating.
• the heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used. Further, it is also preferable to carry out the heating in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon.
• the film after exposure may be subjected to a developing step of developing with a developing solution to form a pattern.
• the method for producing a cured product of the present invention may include a developing step of developing a film exposed by the exposure step with a developing solution to form a pattern.
• a developing step of developing a film exposed by the exposure step with a developing solution to form a pattern By performing the development, one of the exposed portion and the non-exposed portion of the film is removed, and a pattern is formed.
• the development in which the non-exposed portion of the film is removed by the developing process is referred to as negative type development
• the development in which the exposed portion of the film is removed by the developing process is referred to as positive type development.
• Examples of the developing solution used in the developing step include an alkaline aqueous solution or a developing solution containing an organic solvent.
• the developing solution is an alkaline aqueous solution
• examples of the basic compound that the alkaline aqueous solution can contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
• TMAH Tetramethylammonium Hydroxide
• potassium hydroxide sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine , Dimethylethanolamine, Triethanolamine, Tetraethylammonium Hydroxide, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide, Tetrapentyl Ammonium Hydroxide, Tetrahexyl Ammonium Hydroxide, Tetraoctyl Ammonium Hydroxide, Ethyltrimethylammonium Hydroxide , Butyltrimethylammonium Hydroxide, Methyltriamylammonium Hydroxide, Dibutyldipentylammonium Hydroxide, dimethylbis (2-Hydroxyethyl) Ammonium Hydroxide, tri
• the organic solvent may be, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, etc.
• alkyl alkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxy
• Ethyl, etc. methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, etc.
• 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 (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene Glycol monoethyl ether acetate, propylene Glycolmonopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, for example, for example.
• ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-h
• Aromatic hydrocarbons such as toluene, xylene, and anisole, cyclic terpenes such as limonene, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, and diethylene glycol as alcohols.
• Preferable examples thereof include propylene glycol, methylisobutylcarbinol, triethyleneglycol and the like
• examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone and dimethylformamide.
• the developer contains an organic solvent
• one type or a mixture of two or more types of organic solvent can be used.
• a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferable, and cyclopentanone and ⁇ -butyrolactone are preferable.
• a developer containing at least one selected from the group consisting of dimethyl sulfoxide and dimethyl sulfoxide is more preferable, and a developer containing cyclopentanone is most preferable.
• the content of the organic solvent with respect to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more. Is more preferable, and 90% by mass or more is particularly preferable. Further, the content may be 100% by mass.
• the developer may further contain other components.
• other components include known surfactants and known defoaming agents.
• the method of supplying the developing solution is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material on which the film is formed in the developing solution and the method of supplying the developing solution to the film formed on the base material using a nozzle.
• the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
• the method of supplying the developing solution with a straight nozzle or the method of continuously supplying the developing solution with a spray nozzle is preferable. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable. Further, after the developer is continuously supplied by the straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied by the straight nozzle again, and then the base material is spun to use the developer as the base material. A step of removing from the top may be adopted, or this step may be repeated a plurality of times.
• a process in which the developer is continuously supplied to the substrate a process in which the developer is kept in a substantially stationary state on the substrate, and a process in which the developer is superposed on the substrate.
• a process of vibrating with a sound wave or the like and a process of combining them can be adopted.
• the development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
• the temperature of the developing solution at the time of development is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
• the pattern may be further washed (rinsed) with the rinsing solution. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
• the developing solution is an alkaline aqueous solution
• water can be used as the rinsing solution.
• the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water or an organic solvent different from the organic solvent contained in the developer) is used as the rinse solution. be able to.
• the ethers include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate.
• alkyl alkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid) Eth
• 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyl
• Ethylene glycol monomethyl 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 (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether acetate, propionate Lopyrene glycol monopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as cyclic hydrocarbons, for example.
• ketones for example, methyl ethyl ketone, cyclohexanone,
• the rinsing liquid contains an organic solvent
• one type or a mixture of two or more types of organic solvent can be used.
• cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are particularly preferable, cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, PGMEA, PGME are more preferable, and cyclohexanone and PGMEA are preferable. More preferred.
• the rinsing liquid contains an organic solvent
• 50% by mass or more of the rinsing liquid is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is an organic solvent. Is more preferable.
• the rinse liquid may be 100% by mass of an organic solvent.
• the rinse solution may further contain other components.
• other components include known surfactants and known defoaming agents.
• the method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinsing liquid, the method of supplying the rinsing liquid to the base material by filling, and the method of supplying the rinsing liquid to the base material by a shower.
• the method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc. there is a method of supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, the method of supplying with a spray nozzle is more preferable.
• the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
• the rinsing step is preferably a step of supplying the rinsing liquid to the exposed film by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
• a method of supplying the rinse liquid in the rinsing step a step of continuously supplying the rinse liquid to the base material, a step of keeping the rinse liquid in a substantially stationary state on the base material, and a step of superimposing the rinse liquid on the base material.
• a process of vibrating with a sound wave or the like and a process of combining them can be adopted.
• the rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
• the temperature of the rinsing liquid at the time of rinsing is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
• the pattern obtained by the developing step (in the case of performing the rinsing step, the pattern after rinsing) may be subjected to a heating step of heating the pattern obtained by the above-mentioned development. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the developing step. Further, the method for producing a cured product of the present invention may include a pattern obtained by another method without performing a developing step, or a heating step of heating the film obtained by the film forming step. In the heating step, the resin such as the polyimide precursor is cyclized to become the resin such as polyimide.
• the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450 ° C, more preferably 150 to 350 ° C, further preferably 150 to 250 ° C, further preferably 160 to 250 ° C, and particularly preferably 160 to 230 ° C. preferable.
• the heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern by the action of the base or the like generated from the base generator by heating.
• the heating in the heating step 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.
• the temperature rising rate is more preferably 2 to 10 ° C./min, even more preferably 3 to 10 ° C./min.
• the temperature at the start of heating it is preferable to carry out from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. °C / sec is more preferable.
• 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 resin composition of the present invention when applied onto a substrate and then dried, it is the temperature of the film (layer) after drying, for example, from the boiling point of the solvent contained in the resin composition of the present invention.
• the heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
• the heating temperature is preferably 30 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, from the viewpoint of adhesion between layers. It is particularly preferable that the temperature is 120 ° C. or higher.
• the upper limit of the heating temperature is preferably 350 ° C. or lower, more preferably 250 ° C. or lower, and even more preferably 240 ° C. or lower.
• Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 120 ° C. at 3 ° C./min and held at 120 ° C. for 60 minutes, the temperature is raised from 120 ° C. to 180 ° C. at 2 ° C./min, and the temperature is kept at 180 ° C. for 120 minutes. , And so on. Further, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step.
• the pretreatment step may be 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, for example, the first pretreatment step may be performed in the range of 100 to 150 ° C., and then the second pretreatment step may be performed in the range of 150 to 200 ° C. good. Further, 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 carried out in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium or argon or under reduced pressure in order to prevent decomposition of the specific resin.
• the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
• the heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, and an infrared oven.
• the method for producing a cured product of the present invention may include a post-development exposure step for exposing the pattern obtained by the developing step.
• the method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of a heating step and a post-development exposure step.
• the post-development exposure step for example, it is possible to promote a reaction in which the cyclization of the polyimide precursor or the like proceeds by exposure to a photobase generator.
• the post-development exposure step at least a part of the pattern obtained in the development step may be exposed, but it is preferable that all of the above patterns are exposed.
• the exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm 2 and more preferably 100 to 15,000 mJ / cm 2 in terms of exposure energy at a wavelength at which the photosensitive compound has sensitivity. preferable.
• the post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, and it is preferable to use broadband light.
• the pattern obtained by the developing step may be subjected to the metal layer forming step of forming the metal layer on the pattern.
• the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on a pattern obtained by a developing step (preferably one provided in at least one of a heating step and a post-development exposure step). Is preferable.
• metal layer existing metal species can be used without particular limitation, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.
• the method for forming the metal layer is not particularly limited, and an existing method can be applied.
• the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Pat. No. 7,788,181B2, US Pat. No. 9,177,926B2 are used. can do.
• photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and a combination of these can be considered.
• a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned.
• Preferred embodiments of plating include electrolytic plating using a copper sulfate or copper cyanide plating solution.
• the thickness of the metal layer is preferably 0.01 to 50 ⁇ m, more preferably 1 to 10 ⁇ m in the thickest portion.
• Examples of the method for producing a cured product of the present invention or the applicable field of the cured product of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
• Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd.
• the method for producing a cured product of the present invention, or the cured product of the present invention is used for manufacturing a plate surface such as an offset plate surface or a screen plate surface, using it for etching molded parts, and protective lacquer and dielectric in electronics, especially microelectronics. It can also be used for layer production and the like.
• the laminated body of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
• the laminated body of the present invention is a laminated body including two or more layers made of a cured product, and may be a laminated body in which three or more layers are laminated.
• the two or more layers made of the cured product contained in the laminated body at least one is a layer made of the cured product of the present invention, which causes shrinkage of the cured product or deformation of the cured product due to the shrinkage. From the viewpoint of suppressing, it is also preferable that the layer made of all the cured products contained in the laminated body is the layer made of the cured product of the present invention.
• the method for producing a laminated body of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention a plurality of times.
• the laminated body of the present invention contains two or more layers made of a cured product and contains a metal layer between any of the layers made of the cured product.
• the metal layer is preferably formed by the metal layer forming step. That is, it is preferable that the method for producing a laminated body of the present invention further includes a metal layer forming step of forming a metal layer on a layer made of the cured product between the methods for producing a cured product which is performed a plurality of times.
• the preferred embodiment of the metal layer forming step is as described above.
• a laminate including at least a layer structure in which three layers of a layer made of a first cured product, a metal layer, and a layer made of a second cured product are laminated in this order is preferable. Be done. It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention.
• the resin composition of the present invention used for forming the layer composed of the first cured product and the resin composition of the present invention used for forming the layer composed of the second cured product 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.
• the method for producing a laminated body of the present invention preferably 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, (d) a heating step and development are performed again on the surface of a pattern (resin layer) or a metal layer. It is a series of steps including performing at least one of the post-exposure steps in this order. However, at least one of the film forming step (a), the heating step, and the post-development exposure step may be repeated. Further, (e) a metal layer forming step may be included after at least one of the (d) heating step and the post-development exposure step. Needless to say, the laminating step may further include the above-mentioned drying step and the like as appropriate.
• the surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step.
• Plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.
• the laminating step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
• a structure having two or more and 20 or less resin layers such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and a structure having two or more and 9 or less layers is more preferable. ..
• the composition, shape, film thickness, etc. of each of the above layers may be the same or different.
• a cured product (resin layer) of the resin composition of the present invention so as to further cover the metal layer after the metal layer is provided.
• a film forming step an exposure step, (c) a developing step, (d) at least one of a heating step and a post-development exposure step (e) a metal layer forming step is repeated in this order.
• a film forming step an exposure step
• a developing step a developing step
• a metal layer forming step is repeated in this order.
• a film forming step, (d) at least one of a heating step and a post-development exposure step, and (e) a metal layer forming step is repeated in this order.
• the method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a part of the metal layer and the resin composition layer.
• the surface activation treatment step is usually performed after the metal layer forming step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the surface activation treatment of the resin composition layer is performed.
• the metal layer forming step may be performed.
• the surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the exposed resin composition layer, or on the metal layer and the exposed resin composition layer. For both, you may go to at least part of each.
• the surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region of the metal layer that forms the resin composition layer on the surface.
• the surface activation treatment is performed on a part or all of the resin composition layer (resin layer) after exposure. As described above, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activation treatment.
• the resin composition layer when the resin composition layer is cured, such as when negative type development is performed, it is less likely to be damaged by the surface treatment and the adhesion is likely to be improved.
• Specific examples of the surface activation treatment include plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, and CF 4 / O 2 .
• the energy is preferably 500 to 200,000 J / m 2 , more preferably 1000 to 100,000 J / m 2 , and most preferably 10,000 to 50,000 J / m 2 .
• the present invention also discloses a semiconductor device containing the cured product of the present invention or the laminate of the present invention.
• the present invention also discloses a method for producing a cured product of the present invention, or a method for producing a semiconductor device including a method for producing a laminate of the present invention.
• the semiconductor device in which the resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer the description in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-0273557 can be referred to. These contents are incorporated in the present specification.
• CS-6 to CS-15 were synthesized in the same manner except that the methacrylic acid chloride was changed to another acid halide or isocyanate compound in the synthesis of CS-5.
• the structures of CS-6 to CS-15 are shown in the following formulas (CS-6) to (CS-15).
• CS-25 to CS-27 As the bismuth catalyst, the trade name: Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) was used, and CS-25 to CS-27 were prepared by the same method as CS-1 described above except that the reaction temperature was set to 50 ° C. Synthesized.
• the structures of CS-25 to CS-27 are shown in the following formulas (CS-25) to (CS-27).
• CS-28 was synthesized by the same method as CS-5 described above.
• CS-29 was synthesized by the same method as CS-1 described above.
• CS-30 to CS-31 were synthesized by the same method as CS-16 described above.
• the structures of CS-28 to CS-31 are shown in the following formulas (CS-28) to (CS-31).
• the polybenzoxazole precursor resin was filtered off, stirred again in 6 liters of water for 30 minutes and filtered again. Then, the obtained polybenzoxazole precursor resin was dried under reduced pressure at 45 ° C. for 3 days to obtain a polybenzoxazole precursor A-1.
• the structure of the polybenzoxazole precursor A-1 is presumed to be the structure represented by the following formula (A-1).
• polyimide A-2 was a structure represented by the following formula (A-2).
• reaction solution was diluted with 600 mL of ethyl acetate (CH 3 COOEt), transferred to a separating funnel, and washed with 300 mL of water, 300 mL of saturated sodium bicarbonate water, 300 mL of dilute hydrochloric acid, and 300 mL of saturated saline solution in this order.
• ethyl acetate CH 3 COOEt
• 300 mL of water, 300 mL of saturated sodium bicarbonate water, 300 mL of dilute hydrochloric acid, and 300 mL of saturated saline solution in this order.
• drying with 30 g of magnesium sulfate, concentration using an evaporator, vacuum drying, and 61.0 g of dinitro compound (A-1) were obtained in a flask equipped with a condenser and a stirrer, and reduced iron (Fuji Film). Wako Pure Chemical Industries, Ltd.
• a polyimide precursor (A-4) was obtained in the same manner as in ⁇ 5. The weight average molecular weight of this polyimide precursor was 23,500.
• the structure of A-4 is presumed to be the structure represented by the following formula (A-4).
• the obtained polyimide precursor resin was dried at 45 ° C. for 3 days under reduced pressure to obtain a polyimide precursor (A-5).
• the obtained polyimide precursor A-5 had a weight average molecular weight of 23,800 and a number average molecular weight of 10,400.
• the structure of A-5 is presumed to be the structure represented by the following formula (A-5).
• the polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Then, the obtained polyimide precursor resin was dried at 45 ° C. for 2 days under reduced pressure to obtain a polyimide precursor (A-8).
• the obtained polyimide precursor A-8 had a weight average molecular weight of 30,100 and a number average molecular weight of 13,800.
• the structure of A-8 is presumed to be the structure represented by the following formula (A-8).
• ⁇ Synthesis of comparative compound C-1> 10.24 g (110 mmol) of aniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 100 g of terrorahydrofuran in a flask equipped with a stirrer and a condenser, and cooled to 10 ° C. Then, 11.9 g (100 mmol) of phenyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour, and the mixture was stirred at 25 ° C. for 2 hours.
• Examples and comparative examples> In each example, the components listed in the table below were mixed to obtain each resin composition. Further, in each comparative example, the components shown in the following table were mixed to obtain each comparative composition. Specifically, the content of each component described in the table is the amount (parts by mass) described in the column of "addition amount" in each column of the table. The obtained resin composition and comparative composition were pressure-filtered using a filter made of polytetrafluoroethylene having a pore width of 0.5 ⁇ m. Further, in the table, the description of "-" indicates that the composition does not contain the corresponding component.
• [Base generator] -D-1 to D-2 Compounds with the following structure-D-3: WPBG-027 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• SR-209 SR-209 (manufactured by Sartmer)
• SR-231 SR-231 (manufactured by Sartmer)
• SR-239 SR-239 (manufactured by Sartmer)
• ADPH Dipentaerythritol hexaacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
• G-1 1,4-benzoquinone
• G-2 4-methoxyphenol
• G-3 1,4-dihydroxybenzene
• G-4 a compound having the following structure
• DMSO / GBL dimethyl sulfoxide-GBL: ⁇ -butyrolactone-NMP: N-methylpyrrolidone
• the resin composition layer (resin layer) after the exposure is heated at a heating rate of 10 ° C./min under a nitrogen atmosphere to reach the temperature described in the "Temperature” column of the “Curing conditions” in the table. After that, it was heated for 3 hours.
• 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 is subjected to a tensile tester (Tensilon) at a crosshead speed of 300 mm / min in an environment of 25 ° C. and 65% RH (relative humidity) in accordance with JIS-K6251.
• the breaking elongation rate in the longitudinal direction was measured.
• the evaluation was carried out 5 times each, and the arithmetic mean value of the elongation rate (breaking elongation rate) when the test piece broke was used as an index value.
• the above index values were evaluated according to the following evaluation criteria, and the evaluation results are described in the "break elongation" column of the table. It can be said that the larger the index value is, the better the film strength (breaking elongation) of the obtained cured film is.
• evaluation criteria A: The above index value was 60% or more.
• B The index value was 55% or more and less than 60%.
• C The above index value was 50% or more and less than 55%.
• D The above index value was less
• Each resin composition or comparative composition prepared in each Example and Comparative Example was applied onto a silicon wafer by a spin coating method to form a resin composition layer.
• the silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a resin composition layer having a uniform thickness of 15 ⁇ m on the silicon wafer.
• the resin composition layer on the silicon wafer was completely exposed to the entire surface with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed resin composition layer (resin layer) was subjected to a nitrogen atmosphere.
• the temperature was raised at a heating rate of 10 ° C./min and heated at the temperature described in the "Temperature” column of “Curing Conditions” in the table for 180 minutes to obtain a cured layer (resin layer) of the resin composition layer. ..
• the obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
• Chemical solution Mixture of dimethylsulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 90:10 (mass ratio)
• Evaluation conditions Immerse the resin layer in the chemical solution at 75 ° C. for 15 minutes before and after immersion. The dissolution rate (nm / min) was calculated by comparing the film thicknesses of the above.
• the film thickness was measured at 10 points on the coated surface with an ellipsometer (KT-22 manufactured by Foothill), and the film thickness was determined as the arithmetic mean value.
• the evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the "Chemical resistance" column of the table. It can be said that the smaller the dissolution rate, the better the chemical resistance.
• C The dissolution rate was 300 nm / min or more and less than 400 nm / min.
• D The dissolution rate was 400 nm / min or more.
• the developer solubility evaluation was carried out as follows. Each resin composition or comparative composition prepared in each Example and Comparative Example was applied onto a silicon wafer by a spin coating method to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform resin composition layer having a thickness of 35 ⁇ m on the silicon wafer. The resin 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 above exposure was performed using a binary mask having a 1: 1 line-and-space pattern having a width of 50 ⁇ m, a width of 70 ⁇ m, or a width of 100 ⁇ m.
• solvent cyclopentanone
• cyclopentanone at 30 ° C. is used as the developer for the resin composition layer after exposure.
• the shower was developed and rinsed with PGMEA (propylene glycol monomethyl ether acetate).
• TMAH alkali
• the cured film made of the resin composition according to the present invention has excellent chemical resistance.
• the comparative compositions according to Comparative Examples 1 to 4 do not contain compound A. It can be seen that the cured film made of such a comparative composition is inferior in chemical resistance.
• Example 101 The resin composition used in Example 1 was applied in a layered manner on the surface of the copper thin layer of the resin base material having the copper thin layer formed on the surface by a spin coating method, dried at 100 ° C. for 4 minutes, and subjected to a film thickness. After forming a 20 ⁇ m resin composition layer, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m) at a wavelength of 365 nm. After the exposure, it was heated at 100 ° C. for 4 minutes.
• the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained at 230 ° C. for 3 hours to form an interlayer insulating film for the rewiring layer.
• the interlayer insulating film for the rewiring layer was excellent in insulating property. Moreover, when 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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