WO2021132578A1 - Curable resin composition, cured film, layered product, method for producing cured film, and semiconductor device - Google Patents
Curable resin composition, cured film, layered product, method for producing cured film, and semiconductor device Download PDFInfo
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- WO2021132578A1 WO2021132578A1 PCT/JP2020/048779 JP2020048779W WO2021132578A1 WO 2021132578 A1 WO2021132578 A1 WO 2021132578A1 JP 2020048779 W JP2020048779 W JP 2020048779W WO 2021132578 A1 WO2021132578 A1 WO 2021132578A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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- 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
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
Definitions
- the present invention relates to a curable resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.
- Resins such as polyimide and polybenzoxazole are applied to various applications because they have excellent heat resistance and insulating properties.
- the above application is not particularly limited, and examples of a semiconductor device for mounting include use as a material for an insulating film and a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.
- resins such as polyimide and polybenzoxazole are used in the form of a curable resin composition containing these resins themselves or a curable resin composition containing a precursor of these resins.
- a cured resin can be formed on the base material by applying such a curable resin composition to the base material by, for example, coating, and then exposing, developing, heating, etc., if necessary. ..
- the curable 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 curable resin composition to be applied. It can be said that it has excellent adaptability.
- industrial application development of curable resin compositions containing resins such as polyimide and polybenzoxazole or precursors thereof is expanding. It is expected more and more.
- Patent Document 1 describes (A) photosensitive resin: 100 parts by mass, (B) photosensitive agent: 1 to 40 parts by mass, (C) copper discoloration inhibitor: 0.05 to 20 parts by mass, and (D). ) A photosensitive resin composition containing a solvent and having a water content of 0.6 to 10% by mass in the photosensitive resin composition is described.
- the cured film containing polyimide or polybenzoxazole is used, for example, in the above-mentioned insulating film, encapsulant material, protective film, flexible substrate base film, coverlay, and the like.
- a curable resin composition capable of obtaining a cured film excellent in suppressing corrosion of metals such as copper used for wiring and the like.
- the present invention relates to a curable resin composition capable of obtaining a cured film excellent in suppressing corrosion of adjacent metals, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and the cured film. It is an object of the present invention to provide a method for producing the above and a semiconductor device containing the cured film or the laminate.
- ⁇ 1> At least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.
- Compounds having a triazole structure, as well as Contains solvent, A curable resin composition in which the pH of the composition is less than 7.0.
- ⁇ 2> The curable resin composition according to ⁇ 1>, wherein the pKa in dimethyl sulfoxide of the compound having a triazole structure is less than 15.
- ⁇ 3> The curable resin composition according to ⁇ 1> or ⁇ 2>, wherein the compound having a triazole structure contains a compound having a 1,2,3-triazole structure.
- ⁇ 4> The curable resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the compound having a triazole structure contains a compound having a benzotriazole structure.
- ⁇ 6> The curable resin composition according to any one of ⁇ 1> to ⁇ 5>, which contains a solvent containing no nitrogen atom as the solvent.
- ⁇ 7> The curable resin composition according to any one of ⁇ 1> to ⁇ 6>, which comprises a solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms as the solvent.
- ⁇ 8> The curable resin composition according to any one of ⁇ 1> to ⁇ 7>, which is used for forming an interlayer insulating film for a rewiring layer.
- ⁇ 9> A cured film obtained by curing the curable resin composition according to any one of ⁇ 1> to ⁇ 8>.
- ⁇ 10> A laminate containing two or more layers of the cured film according to ⁇ 9> and containing a metal layer between any of the cured films.
- a method for producing a cured film which comprises a film forming step of applying the curable resin composition according to any one of ⁇ 1> to ⁇ 8> to a substrate to form a film.
- the method for producing a cured film according to ⁇ 11> which comprises an exposure step of exposing the film and a developing step of developing the film.
- the method for producing a cured film according to ⁇ 11> or ⁇ 12> which comprises a heating step of heating the film at 50 to 450 ° C.
- a semiconductor device comprising the cured film according to ⁇ 9> or the laminate according to ⁇ 10>.
- a curable resin composition capable of obtaining a cured film excellent in suppressing corrosion of adjacent metals, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, the above.
- a method for producing a cured film and a semiconductor device including the cured film or the laminate are provided.
- the present invention is not limited to the specified embodiments.
- the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
- the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
- the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
- the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- exposure includes not only exposure using light but also exposure using particle beams such as an electron beam and an ion beam. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
- (meth) acrylate means both “acrylate” and “methacrylate”, or either
- (meth) acrylic means both “acrylic” and “methacryl”, or
- Either, and "(meth) acryloyl” means both “acryloyl” and “methacryloyl”, or either.
- Me in the structural formula represents a methyl group
- Et represents an ethyl group
- Bu represents a butyl group
- Ph represents a phenyl group.
- the total solid content means the total mass of all the components of the composition excluding the solvent.
- the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
- GPC measurement gel permeation chromatography
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
- the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as “upper”.
- the opposite direction is referred to as "down”.
- the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component.
- the content of each component in the composition means the total content of all the compounds corresponding to the component.
- the temperature is 23 ° C.
- the atmospheric pressure is 101,325 Pa (1 atm)
- the relative humidity is 50% RH.
- the combination of preferred embodiments is a more preferred embodiment.
- the curable resin composition of the present invention (hereinafter, also simply referred to as “the composition of the present invention”) is triazole, at least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof. It contains a compound having a structure and a solvent, and the pH of the composition is less than 7.0.
- at least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof is also referred to as "specific resin”.
- the cured film containing polyimide or polybenzoxazole is used in various devices, for example, as an insulating film, a material for a sealing material, a protective film, a base film for a flexible substrate, a coverlay, and the like.
- corrosion of the metal at a portion where a metal such as copper used as wiring or the like in a device and a cured film is in contact may become a problem.
- the present inventors have found that such metal corrosion is related to the acidity of the composition used for forming the cured film.
- the present inventors migrate metal such as copper into the composition as ions, and the components in the cured film or water, oxygen, or water supplied from the outside of the cured film, or It is speculated that it reacts with halogens to form fragile copper compounds and corrosion progresses.
- the composition of the present invention it is excellent in the ability to suppress corrosion of a compound having a triazole structure and a metal such as copper even under high temperature and high humidity conditions (for example, conditions such as 150 ° C. and 90% RH relative humidity). .. Further, according to the composition of the present invention, for example, even when the cured film and the metal are exposed to high temperature conditions, voids (voids) at the interface between the metal and the cured film due to the corrosion suppressing effect of the metal. ) Is considered to be suppressed.
- the cyclization of the polyimide precursor and the polybenzoxazole precursor is suppressed by setting the pH to less than 7, and thus the liquid of the composition. It is considered to have excellent storage stability. Further, in the composition containing polyimide or polybenzoxazole, when the pH is set to less than 7, main chain breakage (that is, decrease in molecular weight) due to hydrolysis is less likely to occur, and the composition is excellent in liquid storage stability. Conceivable.
- Patent Document 1 does not describe or suggest that the pH of the curable resin composition containing the specific resin is within the specific range.
- the curable resin composition of the present invention will be described in detail.
- the pH of the curable resin composition of the present invention is less than 7.0, preferably 6.8 or less, preferably 6.5 or less, from the viewpoint of metal corrosion inhibition and storage stability of the composition. It is more preferable, it is more preferably 6.2 or less, and it is particularly preferable that it is 6.0 or less.
- the lower limit of the pH is not particularly limited, but is preferably 2.0 or higher, more preferably 3.0 or higher, further preferably 4.0 or higher, and preferably 4.5 or higher. It is particularly preferable, and most preferably 5.0 or more.
- the electrode of the above device is immersed in a 3.33 mmol / L potassium chloride (KCl) solution.
- the composition is diluted with the solvent contained in the composition, and the pH is measured. The above measurement is performed at least at three points where the dilution ratio is changed.
- Example 1 the pH calculation method in Example 1 described later will be described.
- Table 1 in the curable resin composition used in Example 1, log 10 (dilution ratio) of the dilution ratio when the dilution ratio (mass ratio) is 3, 30, and 300 times, and each dilution.
- the pH (measured value) of the subsequent solution is described.
- the pH of the composition is determined by, for example, selection of a solvent, use of an acidic resin (for example, polyimide having an acid group, polybenzoxazole having an acid group, or a precursor thereof and a resin having an acid group). It is adjusted by using a pH adjuster, adjusting the content of a compound having a triazole structure, or a combination of these methods.
- an acidic resin for example, polyimide having an acid group, polybenzoxazole having an acid group, or a precursor thereof and a resin having an acid group. It is adjusted by using a pH adjuster, adjusting the content of a compound having a triazole structure, or a combination of these methods.
- the curable resin composition of the present invention contains a compound having a triazole structure.
- a compound having a triazole structure is also referred to as a “specific compound”.
- the number of triazole structures in the specific compound may be 1 or more, preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and preferably 1.
- the triazole structure is an aromatic 5-membered ring structure containing three nitrogen atoms, and may be a 1,2,3-triazole structure or a 1,2,4-triazole structure. However, from the viewpoint of suppressing metal corrosion, a 1,2,3-triazole structure is preferable.
- the 1,2,3-triazole structure has a structure represented by the following formula (T-1), and the 2H-1,2,3 triazole structure has a structure represented by the following formula (T-2).
- T-1 The 1H-1,2,3 triazole structure
- T-2 the 2H-1,2,3 triazole structure
- T-3 Examples of the 1,2,4 triazole structure include structures represented by the following formula (T-3).
- # and * each represent a binding site with a hydrogen atom or another structure.
- the triazole structure in the specific compound a structure represented by any of the formula (T-1), the formula (T-2) and the formula (T-3) is preferable, and from the viewpoint of suppressing metal corrosion, the above formula is described below.
- the structure represented by either (T-1) or (T-2) is more preferable.
- the pKa in dimethyl sulfoxide (DMSO) of the specific compound is preferably less than 15, more preferably 8 or more and less than 15, and further preferably 10 or more and less than 15. It is particularly preferably 10 or more and 14 or less.
- pKa represents the logarithm of the reciprocal of the first dissociation constant of acid, and the Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; compilation: Braude).
- the specific compound preferably contains a compound represented by any of the following formulas (T1-1) to (T1-3) or a salt thereof, and is preferably represented by the formula (T1-1) or the formula (T1-2). It is more preferable to contain the compounds represented or salts thereof.
- R 11 and R 12 independently represent a hydrogen atom or a monovalent substituent
- R 21 and R 22 independently represent a hydrogen atom or 1 respectively.
- R 31 and R 32 each independently represent a valent substituent
- RN 1 , RN 2 and RN 3 each represent a hydrogen atom or a monovalent substituent, R 11 .
- R 12 may form at least two members ring structure of R N1, may be formed at least two bonded ring structure of R 21, R 22, R N2 , R 31, At least two of R 32 and RN 3 may be combined to form a ring structure.
- R 11 and R 12 are preferably hydrogen atoms or hydrocarbon groups, respectively, and more preferably hydrocarbon groups.
- the hydrocarbon group is not particularly limited, but an aliphatic hydrocarbon group or an aromatic hydrocarbon group is preferable, and an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable. More preferred.
- R N1 represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom. Examples of the monovalent substituent described above include the same groups as the hydrocarbon groups represented by R 11, preferable embodiments thereof are also the same.
- R 11 and R 12 are bonded to form a ring structure.
- the ring structure may be any of an aliphatic hydrocarbon ring structure, an aromatic hydrocarbon ring structure, an aliphatic heterocyclic structure, and an aromatic heterocyclic structure, and the pKa in the DMSO of the specific compound is described above. From the viewpoint of the range, the aromatic hydrocarbon ring structure is preferable. Examples of the aliphatic hydrocarbon ring structure include an aliphatic hydrocarbon ring structure having 4 to 20 carbon atoms.
- Examples of the aromatic hydrocarbon ring structure include an aromatic hydrocarbon ring structure having 6 to 20 carbon atoms, and a benzene ring structure is preferable.
- Examples of the aliphatic heterocyclic structure include an aliphatic heterocyclic structure having 5 to 20 ring members.
- Examples of the complex atom in the above aliphatic heterocyclic structure include a nitrogen atom, an oxygen atom, a sulfur atom and the like.
- Examples of the aromatic heterocyclic structure include an aromatic heterocyclic structure having 5 to 20 ring members.
- Examples of the complex atom in the above aliphatic heterocyclic structure include a nitrogen atom, an oxygen atom, a sulfur atom and the like.
- each R 21, R 22 and R N2 have the same meaning as R 11, R 12 and R N1 in the formula (T1-1), preferable embodiments thereof are also the same.
- each R 31, R 32 and R N3, have the same meaning as R 11, R 12 and R N1 in the formula (T1-1), preferable embodiments thereof are also the same.
- the salt of the compound represented by any of the formulas (T1-1) to (T1-3) include known inorganic salts such as sodium salt, potassium salt and magnesium salt, or tetrabutylphosphonium salt and the like. Known organic salts of.
- the specific compound preferably contains a compound having a benzotriazole structure.
- the benzotriazole structure refers to a structure in which the above-mentioned triazole structure and a benzene ring structure form a condensed ring.
- the number of benzotriazole structures in the specific compound may be 1 or more, preferably 1 to 10, more preferably 1 to 4, and 1 or 2. It is more preferably present, and particularly preferably 1.
- the specific compound When the specific compound has a benzotriazole structure, it may have only a benzotriazole structure as a triazole structure, or may have a benzotriazole structure and a triazole structure other than the benzotriazole structure.
- Examples of the 1H-benzotriazole structure include a structure represented by the following formula (T-4), and examples of the 2H-benzotriazole structure include a structure represented by the following formula (T-5).
- # and * represent a binding site with a hydrogen atom or another structure, respectively.
- Equation (T1-4) and Equation (T1-5) When the specific compound is a compound having a benzotriazole structure, the specific compound preferably contains a compound represented by any of the following formulas (T1-4) and (T1-5) or a salt thereof.
- R 41 , R 42 , R 43 and R 44 each independently represent a hydrogen atom or a monovalent substituent, R 51 , R 52 , R 53.
- R 54 each independently represent a hydrogen atom or a monovalent substituent
- each R N4 and R N5 represent a hydrogen atom or a monovalent substituent
- R 41, R 42, R 43, R 44 and , R N4 may be combined to form a ring structure, or at least two of R 51 , R 52 , R 53 , R 54 and RN 5 may be combined to form a ring structure. Good.
- R 41 , R 42 , R 43 and R 44 are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and the hydrogen atom or the number of carbon atoms.
- Alkyl groups of 1 to 10 are more preferable, alkyl groups having a hydrogen atom or 1 to 4 carbon atoms are particularly preferable, and hydrogen atoms or methyl groups are particularly preferable. From the viewpoint of high temperature stability of the specific compound, it is preferable that at least one of R 41 , R 42 , R 43 and R 44 is a monovalent substituent.
- R N4 represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom.
- Examples of the monovalent substituent include the same group as the hydrocarbon group in R 11 in the above formula (T1-1), and the preferred embodiment is also the same.
- R 41 , R 42 , R 43 , R 44, and RN 4 may be bonded to form a ring structure, but it is preferable not to form a ring structure.
- R 41 , R 42 , R 43 , R 44 and RN 4 when at least two of R 41 , R 42 , R 43 , R 44 and RN 4 are combined to form a ring structure, of R 41 , R 42 , R 43 and R 44 . It is preferable that at least two of them are combined to form a ring structure.
- the ring structure similar to the ring structure and the ring structure at least two are formed by bonding of R 11, R 12, R N1 in the above formula (T1-1) and the like, a preferred embodiment also the same Is.
- R 51 , R 52 , R 53 , R 54 and R N 5 are R 41 , R 42 , R 43 , R 44 and R N 4 in formula (T1-4), respectively. It has the same meaning, and the preferred embodiment is also the same.
- the compound having a triazole structure is not particularly limited, but 1H-benzotriazole, 2H-benzotriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 7-methyl-1H-benzotriazole, tolyl.
- Triazole 5,6-dimethylbenzotriazole, carboxybenzotriazole, 5-chloro-2-methylbenzotriazole, 1-methyl-1H-benzotriazole, 5-nitrobenzotriazole, 1-aminobenzotriazole, 4,5,6 , 7-Tetrabromobenzotriazole, 1H-1,2,3-triazole, 2H-1,2,3-triazole, 1,2,4-triazole, tris (1H-benzotriazole-1-yl) methane, these Examples thereof include benzotriazoles of the above compounds and salts of these compounds.
- the molecular weight of the specific compound is preferably 69 to 1,000, more preferably 69 to 500, and even more preferably 69 to 200.
- the content of the specific compound is preferably 0.1 to 30% by mass with respect to the total solid content of the curable resin composition of the present invention.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is more preferably 20% by mass or less, further preferably 10% by mass or less, particularly preferably 5% by mass or less, and most preferably 3% by mass or less.
- the specific compound one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
- the curable resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.
- the curable resin composition of the present invention preferably contains a polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.
- the specific resin preferably has a radically polymerizable group.
- the curable resin composition preferably contains a photoradical polymerization initiator described later as a photosensitizer, contains a photoradical polymerization initiator described below as a photosensitizer, and is described later.
- the radical cross-linking agent described above it is more preferable to contain the radical cross-linking agent described above, and it is further preferable to contain the photoradical polymerization initiator described below as the photosensitizer, the radical cross-linking agent described below, and the sensitizer described below.
- a curable resin composition for example, a negative type photosensitive layer is formed.
- the specific resin may have a polarity converting group such as an acid-degradable group.
- the curable resin composition preferably contains a photoacid generator described later as a photosensitizer. From such a curable resin composition, for example, a chemically amplified positive type photosensitive layer or a negative type photosensitive layer is formed.
- polyimide precursor The type of the polyimide precursor used in the present invention is not particularly specified, but it is preferable that the polyimide precursor contains a repeating unit represented by the following formula (2). Equation (2) In 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, and R 113. And R 114 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.
- a cyclic aliphatic group of 6 to 20, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
- a group represented by -Ar-L-Ar- is exemplified.
- 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.
- 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 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. It is preferably a diamine containing, and more preferably a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of aromatic groups include:
- diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 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 and 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. 2017/0385898 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. 2017/0385898 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, and 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 a phenylene group is preferably, L is an aliphatic hydrocarbon group having a fluorine atom are carbon atoms and optionally 1 or substituted by 2, -O -, - CO - , - S- or SO 2 - are preferred.
- 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) from the viewpoint of i-ray transmittance.
- a divalent organic group represented by the formula (61) is more preferable.
- Equation (51) In formula (51), R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, methyl group or trifluoro. It is a methyl group.
- 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 independently fluorine atoms or trifluoromethyl groups, respectively.
- Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.
- diamines can also be preferably used.
- 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.
- * represents a binding site with another structure.
- R 112 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- , NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO More preferably, it is a group selected from-, -S- and SO 2- , -CH 2- , -C (CF 3 ) 2- , -C (CH 3 ) 2-, -O-, -CO. It is more preferably a divalent group selected from the group consisting of-, -S- and SO 2-.
- R 115 examples include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
- the tetracarboxylic dianhydride is preferably represented by the following formula (O). Equation (O) In formula (O), R 115 represents a tetravalent organic group.
- a preferred range of R 115 has the same meaning as R 115 in formula (2), and preferred ranges are also the same.
- tetracarboxylic dianhydride examples include pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-.
- PMDA pyromellitic dianhydride
- 3,3', 4,4'-biphenyltetracarboxylic dianhydride 3,3', 4,4'-.
- tetracarboxylic 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 each independently represent a hydrogen atom or a monovalent organic group, and it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and both contain a polymerizable group.
- the polymerizable group is a group capable of a cross-linking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferable.
- 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, a methylol group and an amino.
- the group is mentioned.
- a group having an ethylenically unsaturated bond is preferable.
- Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
- R200 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
- R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- or a polyalkyleneoxy group. Examples of suitable R 201 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group.
- the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
- the alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
- the arrangement 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. Is more preferable, 2 to 5 is more preferable, 2 to 4 is more preferable, 2 or 3 is particularly preferable, and 2 is most preferable.
- the said 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 polytrimethyleneoxy 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 in which an oxy group is bonded 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 and R 114 are independently hydrogen atoms or monovalent organic groups.
- the monovalent organic group include an aromatic group and an aralkyl group in which an acidic group is bonded to one, two or three carbons constituting the aryl group, preferably one.
- Specific examples thereof include an aromatic group having an acidic group having 6 to 20 carbon atoms and an aralkyl group having an acidic group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned.
- the acidic group is preferably an OH group. It is also more preferable that R 113 or R 114 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.
- R 113 or R 114 is preferably a monovalent organic group.
- the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
- the alkyl group preferably has 1 to 30 carbon atoms.
- the alkyl group may be linear, branched or cyclic.
- linear or branched alkyl group examples include 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, a dodecyl group, a tetradecyl group and an octadecyl group.
- Isobutyl group isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2- (2- (2-methoxyethoxy) ethoxy) ethoxy group, 2- (2- (2) -Ethoxyethoxy) ethoxy) ethoxy) ethoxy group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy group, and 2- (2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) Ethoxy group is mentioned.
- the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
- Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
- Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving both high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
- aromatic group examples include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene.
- the benzene ring is most preferable.
- 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.
- At least one of R 113 and R 114 may be a polar converting group such as an acid-degradable group.
- the acid-degradable group is not particularly limited as long as it is decomposed by the action of an acid to produce 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 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, tert-butoxycarbonylmethyl.
- examples include a group and a trimethylsilyl ether group. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.
- the polyimide precursor has a fluorine atom in the structural unit.
- the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
- the polyimide precursor 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 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). With such a structure, the width of the exposure latitude can be further widened. 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 polymerizable groups.
- a 1, A 2, R 111 , R 113 and R 114 each independently have the same meaning as A 1, A 2, R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same .
- R 112 has the same meaning as R 112 in formula (5), and preferred ranges are also the same.
- the polyimide precursor may contain one type of repeating structural unit represented by the formula (2), but may contain two or more types. 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 structural units in addition to the repeating unit of the above formula (2).
- polyimide precursor in the present invention a polyimide precursor in which 50 mol% or more of all repeating units, further 70 mol% or more, particularly 90 mol% or more is a repeating unit represented by the formula (2) is used. Illustrated.
- the weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000.
- 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 polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more.
- the upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly defined, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is further preferable, and 3.2 or less is further preferable. Preferably, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.
- the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
- 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 forming property.
- a polyimide that dissolves is preferable, and a polyimide that dissolves 1.0 g or more is more preferable.
- the upper limit of the dissolution amount is not particularly limited, but is preferably 100 g or less.
- the 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 binding chain among the molecules of the polymer compound constituting the resin, and the “side chain” refers to other binding chains.
- the polyimide preferably 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 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 1 to 50 mol / g, and more preferably 5 to 30 mol / g.
- the polyimide preferably 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 0.01 to 5 mol / g, more preferably 0.05 to 1 mol / g.
- 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 preferably provided at the side chain.
- the ethylenically unsaturated bond preferably has radical polymerization property.
- 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.
- ethylenically unsaturated bond ethylene R 131 in the repeating unit represented by the preferably contained in R 131 in the repeating unit represented by the formula (4) described later, which will be described later Equation (4) 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 which is directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group and a (meth) group.
- Examples thereof include an acryloyloxy group and a group represented by the following formula (IV).
- R 20 represents a hydrogen atom or a methyl group, and a methyl group is preferable.
- a (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.
- 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 201 in the formula (III) is bonded.
- a preferred embodiment of the alkylene group having 2 to 12 carbon atoms in L or the (poly) 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 12 alkylene groups or (poly) alkyleneoxy groups having 2 to 30 carbon atoms.
- X is preferably an oxygen atom.
- * is synonymous with * in 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 obtained by reacting, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate).
- a polyimide having a hydroxy group such as a phenolic hydroxy group
- a compound having a glycidyl group and an ethylenically unsaturated bond for example, glycidyl methacrylate.
- the polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy 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 in which an oxy group is bonded 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.
- * represents a bonding site with another structure, and is preferably a bonding 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 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g. From the viewpoint of production suitability, the amount of ethylenically unsaturated bonds with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and preferably 0.0005 to 0.05 mol / g. More preferred.
- the polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.
- the crosslinkable group other than the ethylenically unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
- the crosslinkable group other than the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by the formula (4) described later, for example.
- the amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g. From the viewpoint of production suitability, the amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. It is more preferably g.
- the polyimide may have a polarity converting group such as an acid-degradable group.
- the acid-degradable group in the polyimide is the same as the acid-degradable 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 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 the 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 2 to 35 mgKOH / g, and 3 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.
- 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.
- 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 ring, but preferably contains a repeating unit represented by the following formula (4), and is represented by the formula (4). More preferably, it is a compound containing a repeating unit and having a polymerizable group.
- Equation (4) In formula (4), R 131 represents a divalent organic group and R 132 represents a tetravalent organic group. When having a polymerizable 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 (4-1) In formula (4-1), R133 is a polymerizable group, and the other groups are synonymous with formula (4). 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).
- the polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group possessed by the polyimide precursor and the like.
- R 131 represents a divalent organic group. Examples of the divalent organic group include those similar to R 111 in the formula (2), and the preferred range is also the same. Further, as R 131 , a diamine residue remaining after removal of the amino group of the diamine can be mentioned. Examples of the diamine include aliphatic, cyclic aliphatic or aromatic diamines. Specific examples include an example of R 111 in the polyimide precursor formula (2).
- 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 occurrence of warpage during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains and / or both of propylene glycol chains in one molecule, and more preferably, it is a diamine residue containing no aromatic ring.
- R 132 represents a tetravalent organic group.
- examples of the tetravalent organic group include those similar to R 115 in the formula (2), and the preferred range is also the same.
- R 132 includes a tetracarboxylic acid residue remaining after removal of an anhydride group from the tetracarboxylic dianhydride.
- Specific examples include an example of R 115 in the polyimide precursor formula (2).
- R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
- R 131 and R 132 has an OH group. 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 preferable examples. As R 132 , the above (DAA-1) to (DAA-5) are more preferable examples.
- the polyimide has a fluorine atom in the structural unit.
- the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and 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 polyimide may be sealed with an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound.
- an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound.
- monoamine acid anhydride
- monocarboxylic acid monoacid chloride compound or monoactive ester compound.
- monoactive ester compound preferable.
- monoamine 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 by, for example, 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 contain repeating structural units of the above formula (4), all containing one type of R 131 or R 132, and the above formula (4) containing two or more different types of R 131 or R 132. May include repeating units of. Further, the polyimide may contain other types of repeating structural units in addition to the repeating unit of the above formula (4).
- Polyimide is, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound (partially replaced with a terminal encapsulant which is monoamine) at a low temperature, or a tetracarboxylic acid dianhydride (partly an acid) at a low temperature.
- a polyimide precursor is obtained by using a method such as a method of reacting with an end-capping agent (replaced with an end-capping agent), and the polyimide precursor is completely imidized by using a known imidization reaction method, or an imide in the middle.
- Synthesis using a method of stopping the conversion reaction and introducing a partially imidized structure and further, a method of introducing a partially imidized structure by blending a completely imidized polymer with its polyimide precursor.
- a method of introducing a partially imidized structure by blending a completely imidized polymer with its polyimide precursor.
- Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by HUNTSMAN Co., Ltd.).
- the weight average molecular weight (Mw) of the polyimide is 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and 10,000 to 30,000. More preferred. 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 polyimides are contained, it is preferable that the weight average molecular weight of at least one kind of polyimide is in the above range.
- 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).
- Equation (3) R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group. Represent.
- 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 composed 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, further 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-Dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadiponic acid, 3-methyladiponic acid, pimelli acid, 2,2,6,6-tetramethylpimeric acid, suberin Acid, dodecafluorosveric acid, azelaic acid, sebacic acid, hexa
- 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 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- Represents a divalent group selected from the group consisting of, and each independently represents a binding site with another structure.
- 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 the bisaminophenol derivative include 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 binding sites with the nitrogen atom to which R 122 in the formula (3) is bonded, and preferably R 122 in another 2 Exemplary ethynylphenylbiadamantane derivatives (3) is a binding site to the oxygen atom bonding, two * is a bond sites with an oxygen atom R 122 are attached in the formula (3) , And two # are the binding sites with the nitrogen atom to which R 122 in the formula (3) is bound, or two * are the binding sites with the nitrogen atom to which R 122 in the formula (3) is bound.
- the site is a site and the two #s are the binding sites with the oxygen atom to which 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 the binding site is a binding site with an atom and the two #s are the binding sites with a nitrogen atom to which R 122 in the formula (3) is bonded.
- 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.
- 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 alkylene 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 a well-balanced polybenzoxazole precursor can be obtained.
- the polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3). It is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit in that the occurrence of warpage due to ring closure can be suppressed.
- SL diamine residue represented by the following formula
- 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 dianhydride is used as the repeating structural unit. It is also preferable to include it. 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 preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further, when used in the compositions described below. It is preferably 22,000 to 28,000.
- 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, and further 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, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. Is more preferable, and 2.2 or less is even more preferable.
- 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. Further, it may be a compound represented by the following formula (X) and having a polarity converting group such as an acid-degradable group. In formula (X), R 133 represents a divalent organic group and R 134 represents a tetravalent organic group.
- the polar converting group such as a polymerizable group or an acid-degradable group may be located at at least one of R 133 and R 134 , and may be located at least one of the following. It may be located at the end of the polybenzoxazole as shown in the formula (X-1) or the formula (X-2). Equation (X-1) In formula (X-1), at least one of R 135 and R 136 is a polar converting group such as a polymerizable group or an acid-degradable group, and is not a polar converting group such as a polymerizable group or an acid-degradable group.
- R 137 is a polar converting group such as a polymerizable group or an acid-degradable group, the other is a substituent, and the other group is synonymous with the formula (X).
- a polar converting group such as a polymerizable group or an acid-degradable group is synonymous with the polymerizable group described in the polymerizable group possessed by the above-mentioned polyimide precursor or the like.
- R 133 represents a divalent organic group.
- the divalent organic group include an aliphatic or 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 condensed ring.
- R 134 when R 134 is the following organic group, it forms the following structure.
- Polybenzoxazole preferably has an oxazoleization rate of 85% or more, and more preferably 90% or more.
- the oxazoleization rate is 85% or more, the membrane shrinkage due to ring closure that occurs when oxazoled by heating is reduced, and the occurrence of warpage can be suppressed more effectively.
- Polybenzoxazole everything may include repeating structural units of formula (X) comprising one of R 131 or R 132, 2 or more different types of R 131 or the formula comprising R 132 ( It may include the repeating unit of X). Further, the polybenzoxazole may contain other types of repeating structural units in addition to the repeating unit of the above formula (X).
- the resulting polybenzoxazole for example, a bis-aminophenol derivative, a dicarboxylic acid or the dicarboxylic acid containing R 133, is reacted with a compound selected from such dicarboxylic acid dichloride and dicarboxylic acid derivatives, the polybenzoxazole precursor ,
- a compound selected from such dicarboxylic acid dichloride and dicarboxylic acid derivatives the polybenzoxazole precursor .
- This is obtained by oxazoleization using a known oxazoleization reaction method.
- a dicarboxylic acid an active ester-type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance 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, and even 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.
- a polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine.
- the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent such as thionyl chloride and then reacting it with a diamine.
- non-halogen catalyst a known amidation catalyst containing no halogen atom can be used without particular limitation.
- a boroxin compound, an N-hydroxy compound, a tertiary amine, a phosphoric acid ester, or an amine can be used.
- carbodiimide compounds such as salts and urea compounds.
- the carbodiimide compound include N, N'-diisopropylcarbodiimide, N, N'-dicyclohexylcarbodiimide and the like.
- the organic solvent may be one kind or two or more kinds.
- the organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
- the polyimide may be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (for example, promotion of cyclization reaction by acting a catalyst), or directly. , Polyimide may be synthesized.
- the end of the polyimide precursor, etc. is used as an end sealant such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. It is preferable to seal. It is more preferable to use monoamine as the terminal encapsulant, and preferred compounds of monoamine are aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-.
- a step of precipitating a solid may be included in the production of the polyimide precursor or the like.
- the polyimide precursor or the like in the reaction solution is precipitated in water, and the polyimide precursor or the like such as tetrahydrofuran is dissolved in a soluble solvent to cause solid precipitation.
- the polyimide precursor or the like can be dried to obtain a powdery polyimide precursor or the like.
- the content of the specific resin in the 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 composition. More preferably, it is more preferably 50% by mass or more.
- the resin content in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass or less, based on the total solid content of the composition. It is more preferably 97% by mass or less, and even more preferably 95% by mass or less.
- the composition of the present invention may contain only one type of the specific resin, or may contain two or more types of the specific resin. When two or more types are included, the total amount is preferably in the above range.
- 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 phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, and acrylic resins.
- acrylic resins by further adding an acrylic resin, a composition having excellent coatability can be obtained, and a pattern (cured film) having excellent solvent resistance can be obtained.
- the composition is formed by adding an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable base value to the composition in place of the polymerizable compound described later or in addition to the polymerizable compound described later. It is possible to improve the coatability of an object, the solvent resistance of a pattern (cured film), and the like.
- 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 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. preferable.
- 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 70% by mass, based on the total solid content of the composition. % Or less, more 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 preferably 10% by mass or less, based on the total solid content of the composition. More preferably, it is more preferably 5% by mass or less, and even more preferably 1% by mass or less.
- 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 types are included, the total amount is preferably in the above range.
- the curable resin composition of the present invention contains a solvent.
- a solvent a known solvent can be arbitrarily used.
- the solvent is preferably an organic solvent.
- the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, amides, and alcohols.
- the curable resin composition of the present invention preferably has a water content of 5% by mass or less based on the total mass of the solvent from the viewpoints of suppressing coating defects during coating and improving storage stability. ..
- the content of the water is preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.1% by mass or less. Moreover, the content of the said water may be 0 mass%.
- 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, Ethyl ethoxyacetate, etc.)
- 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)
- 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, ethyl 2-alkyl
- ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol.
- Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.
- ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.
- aromatic hydrocarbons for example, toluene, xylene, anisole, limonene and the like are preferable.
- sulfoxides for example, dimethyl sulfoxide is preferable.
- N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferable.
- alcohols 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 mixed solvent to be used is preferable.
- the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
- a combination of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and ⁇ -butyrolactone is also preferable.
- the curable resin composition of the present invention preferably contains a solvent containing no nitrogen atom as the solvent. Since dissociation (deprotonation) of a specific compound is likely to occur in a solvent that does not contain nitrogen atoms, the adhesion energy between the specific compound and the metal when the composition is applied to the substrate is likely to increase, and the corrosion suppressing ability is excellent. It is considered easy.
- the solvent having no nitrogen atom include the above-mentioned esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.
- ethyl lactate, ⁇ -butyrolactone, dimethylsulfoxide, cyclopentanone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 3-methoxybutyl acetate (3-MBA), methyl-3- Methoxypropionate (MMP), ethyl pyruvate (ethyl pyruvate, EP), 2-ethoxyethyl acetate (EA), n-butyl acetate (BA), or propylene glycol monopropyl ether (PGP) are preferred. Be done.
- the content of the solvent containing no nitrogen atom with respect to the total mass of the solvent contained in the curable resin composition is 10 to 100% by mass. It is preferably 20 to 100% by mass, more preferably 50 to 100% by mass. Further, the curable resin composition of the present invention may be in an embodiment that does not substantially contain a solvent containing a nitrogen atom such as N-methylpyrrolidone.
- the content of the solvent containing a nitrogen atom with respect to the total mass of the solvent contained in the curable resin composition is preferably 5% by mass or less, more preferably 3% by mass or less, and 1 It is more preferably mass% or less, and particularly preferably 0.1 mass% or less.
- the minimum value of the content may be 0% by mass.
- the curable resin composition of the present invention preferably contains as a solvent a solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms.
- a solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms is a solvent containing only atoms selected from carbon atoms, oxygen atoms and hydrogen atoms as atoms constituting the solvent, and contains only carbon atoms and hydrogen atoms. It may be a solvent, but a solvent containing a carbon atom, an oxygen atom and a hydrogen atom is preferable.
- the solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms include the above-mentioned esters, ethers, ketones and aromatic hydrocarbons.
- ethyl lactate, ⁇ -butyrolactone, dimethylsulfoxide, cyclopentanone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 3-methoxybutyl acetate (3-MBA), methyl-3- Methoxypropionate (MMP), ethyl pyruvate (ethyl pyruvate, EP), 2-ethoxyethyl acetate (EA), n-butyl acetate (BA), or propylene glycol monopropyl ether (PGP) are preferred. Be done.
- the curable resin composition of the present invention contains a solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms, only carbon atoms, oxygen atoms and hydrogen atoms with respect to the total mass of the solvent contained in the curable resin composition
- the content of the solvent composed of is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and further preferably 50 to 100% by mass.
- the curable resin composition of the present invention may be in a mode that substantially does not contain a solvent containing atoms other than carbon atoms, oxygen atoms and hydrogen atoms.
- the content of the solvent containing atoms other than carbon atom, oxygen atom and hydrogen atom with respect to the total mass of the solvent contained in the curable resin composition is preferably 5% by mass or less, preferably 3% by mass. It is more preferably less than or equal to, more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less.
- the minimum value of the content may be 0% by mass.
- the content of the solvent is preferably such that the total solid content concentration of the curable resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferable that the amount is 10 to 70% by mass, and more preferably 40 to 70% by mass.
- the solvent content may be adjusted according to the desired thickness and coating method.
- the curable 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 curable resin composition of the present invention may further contain a pH adjuster.
- the pH adjuster include acidic compounds and basic compounds.
- the curable resin composition of the present invention contains at least one selected from the group consisting of an acidic compound and a basic compound, so that an acid or a base enters from the outside of the composition or the cured film.
- the buffering action of these compounds makes it easier for the pH of the composition or the cured film to be kept below 7, and makes it easier to improve the metal corrosion inhibitory property and the liquid storage stability of the composition.
- Examples of the acidic compound include compounds having a carboxy group.
- the compound having a carboxy group is not particularly limited, but a silane coupling agent having a carboxy group, which will be described later, or a polyaminocarboxylic acid compound or a salt thereof is preferable.
- the polyaminocarboxylic acid compound or a salt thereof is not particularly limited, but ethylenediaminetetraacetic acid, trans-1,cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, or amine salts thereof, ammonium. Examples include salt.
- the pKa in DMSO of the carboxy group of the compound having the carboxy group is preferably 4 to 20, more preferably 6 to 18, and 6 to 15 Is more preferable.
- the content of the acidic compound with respect to the total solid content of the curable resin composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass, and 0. It is more preferably 5 to 6% by mass.
- the curable resin composition of the present invention may contain only one type of acidic compound, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.
- the curable resin composition of the present invention preferably contains a basic compound as a pH adjuster.
- the basic compound does not include the above-mentioned compound having a triazole structure.
- the basic compound may be a compound corresponding to a thermal acid generator, a photoacid generator, a migration inhibitor, etc., which will be described later, but it does not correspond to these. It is preferably a compound.
- the basic compound is not particularly limited as long as it is a compound exhibiting basicity in the curable resin composition, but the pKa of the conjugate acid in DMSO is preferably 1.0 to 7.0. , 1.5 to 7.0, more preferably 2.0 to 7.0.
- a compound containing at least one structure selected from the group consisting of an aromatic amine structure and an alcoholic hydroxyl group is preferable, and a compound containing an aromatic amine structure and an alcoholic hydroxyl group is more preferable.
- the aromatic amine structure means a structure in which an amino group or a substituted amino group is directly bonded to an aromatic ring, and a structure in which a substituted amino group is bonded to an aromatic ring is preferable, and the aromatic ring is disubstituted. It is more preferable that the structure has an amino group bonded thereto.
- the substituent in the substituted amino group or the disubstituted amino group is not particularly limited, but a hydrocarbon group which may have a substituent is preferable, and a hydrocarbon group which has at least an alcoholic hydroxyl group as a substituent is preferable.
- an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is further preferable.
- the substituents in the disubstituted amino group may be the same or different.
- the aromatic amine structure a structure represented by the following formula (A-1) is preferably mentioned.
- * independently represents a binding site with a hydrogen atom or a substituent, and at least one of * represents a binding site with a substituent.
- * represents a binding site with a substituent.
- the benzene ring may have a known substituent or condensed ring within the range in which the effect of the present invention can be obtained.
- the alcoholic hydroxyl group means a hydroxy group directly bonded to a carbon atom that is not a ring member of an aromatic ring, and is preferably a hydroxy group directly bonded to a carbon atom contained in an aliphatic hydrocarbon group. ..
- the basic compound in the present invention has an alcoholic hydroxyl group
- the basic compound is preferably an amine compound having an alcoholic hydroxyl group, and more preferably an aromatic amine compound having a basic compound.
- the amine compound is preferably a tertiary amine compound, and more preferably a tertiary aromatic amine compound.
- Examples of the compound containing at least one structure selected from the group consisting of an aromatic amine structure and an alcoholic hydroxyl group include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, and 2,5-bis (4'-diethylaminobenzal).
- N-phenyl-N'-ethylethanolamine N-phenyldiethanolamine, Np-tolyldiethanolamine, or N-phenylethanolamine is preferable.
- the content of the basic compound with respect to the total solid content of the curable resin composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass, and 0. It is more preferably .5 to 6% by mass.
- the curable resin composition of the present invention may contain only one type of basic compound, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.
- the curable resin composition of the present invention preferably contains a silane coupling agent. Further, the curable resin composition of the present invention preferably has a silane coupling agent having a carboxy group as the silane coupling agent.
- the silane coupling agent having a carboxy group corresponds to the above-mentioned acidic compound.
- silane coupling agent having a carboxy group is not particularly limited, but a compound having a monoalkoxysilyl group, a dialkoxysilyl group or a trialkoxysilyl group and a carboxy group is preferable, and a dialkoxysilyl group or a trialkoxysilyl group And a compound having a carboxy group is more preferable, and a compound having a trialkoxysilyl group and a carboxy group is further preferable.
- the alkoxy group in the monoalkoxysilyl group, the dialkoxysilyl group or the trialkoxysilyl group is not particularly limited, but is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.
- the number of carboxy groups in the silane coupling agent having a carboxy group may be 1 or more, but is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
- the molar amount (mmol / g) of the carboxy group in the silane coupling agent having 1 g of the carboxy group is preferably 3.12 to 12.5 mmol / g, and is 3.12 to 6.25 mmol / g. Is more preferable.
- silane coupling agent having a carboxy group examples include, but are not limited to, the following compounds.
- R represents a methyl group or an ethyl group.
- the content of the silane coupling agent having a carboxy group is preferably 0.1% by mass to 20% by mass, and 0.2% by mass to 10% by mass, based on the total solid content of the curable resin composition. It is preferably 0.5 to 5% by mass, and more preferably 0.5 to 5% by mass.
- the content of the silane coupling agent having a carboxy group is preferably 5 to 80% by mass, preferably 10 to 70% by mass, based on the total mass of the basic compound contained in the curable resin composition. Is more preferable.
- the curable resin composition of the present invention may contain only one type of silane coupling agent having a carboxy group, or may contain two or more types. When two or more kinds of silane coupling agents having a carboxy group are contained, the total is preferably in the above range.
- the curable resin composition of the present invention may contain another silane coupling agent having no carboxy group.
- silane coupling agents include cyclic ether groups such as epoxy group and oxetanyl group, groups having an ethylenically unsaturated bond such as vinyl group, allyl group and methacryloyl group, amino group, hydroxy group and mercapto group.
- examples thereof include a silane coupling agent having a nitrogen-containing aromatic heterocyclic group such as an imidazole structure and an alkylamide group.
- the curable resin composition of the present invention contains another silane coupling agent, it is preferably 0.1% by mass to 20% by mass, preferably 0.2% by mass, based on the total solid content of the curable resin composition. It is preferably from mass% to 10% by mass, and more preferably from 0.5 to 5% by mass.
- the curable resin composition of the present invention may contain only one type of other silane coupling agent, or may contain two or more types. When two or more other silane coupling agents are contained, the total is preferably in the above range.
- the composition of the present invention may further contain another resin (hereinafter, also simply referred to as “other resin”) different from the specific resin.
- other resins include polyamide-imide, polyamide-imide precursor, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, and acrylic resin.
- acrylic resin by further adding an acrylic resin, a composition having excellent coatability can be obtained, and an organic film having excellent solvent resistance can be obtained.
- the composition is formed by adding an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable base value to the composition in place of the polymerizable compound described later or in addition to the polymerizable compound described later. It is possible to improve the coatability of an object, the solvent resistance of an organic film, and the like.
- 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 composition. More preferably, it is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more. ..
- the content of the other resin in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass, based on the total solid content of the composition. It is more preferably less than or equal to, more 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 preferably 10% by mass or less, based on the total solid content of the composition. More preferably, it is more preferably 5% by mass or less, and even more preferably 1% by mass or less.
- the lower limit of the content is not particularly limited, and may be 0% by mass or more.
- the composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.
- the composition of the present invention contains a photosensitizer.
- a photosensitizer a photopolymerization initiator is preferable.
- the composition of the present invention preferably contains a photopolymerization initiator as the photosensitizer.
- the photopolymerization initiator is preferably a photoradical polymerization initiator.
- 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. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
- the composition of the present invention will be described later as a photoradical polymerization initiator.
- It preferably contains a metal element-containing compound. That is, in the present invention, among the metal element-containing compounds described later, those having a radical polymerization initiatoring ability can be used as a photoradical polymerization initiator.
- having the ability to initiate radical polymerization means that free radicals capable of initiating radical polymerization can be generated.
- a wavelength range in which the metal element-containing compound absorbs light and the radically polymerizable monomer does not absorb light can be confirmed by confirming the presence or absence of the disappearance of the radically polymerizable monomer when irradiated with light.
- an appropriate method can be selected depending on the type of radical polymerizable monomer or binder polymer, but for example, it can be confirmed by IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography). Good.
- the composition of the present invention contains a metal element-containing compound or the like having a radical polymerization initiating ability
- the composition of the present invention does not substantially contain a radical polymerization initiator other than the above-mentioned metal element-containing compound.
- the fact that the composition of the present invention does not substantially contain a radical polymerization initiator other than the metal element-containing compound means that the content of the radical polymerization initiator other than the metal element-containing compound is the metal element-containing compound. It is said that it is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.1% by mass, based on the total mass of the above.
- the composition of the present invention may contain the metal element-containing compound and another photoradical polymerization initiator.
- the content of the metal element-containing compound relative to the total content of the metal element-containing compound and the other photoradical polymerization initiator is preferably 20 to 80% by mass, more preferably 30 to 70% by mass.
- an oxime compound described later is preferable.
- 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 the range of about 300 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 as the photoradical polymerization initiator.
- halogenated hydrocarbon derivatives for example, compounds having a triazine structure, compounds having an oxadiazole structure, compounds having a trihalomethyl group, etc.
- acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc.
- paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.
- Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated in the present specification.
- KayaCure DETX manufactured by Nippon Kayaku Co., Ltd.
- Nippon Kayaku Co., Ltd. is also preferably used.
- a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.
- IRGACURE 184 (IRGACURE is a registered trademark)
- DAROCUR 1173 As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.
- aminoacetophenone-based initiator commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
- the compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
- acylphosphine-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.
- the metallocene compound examples include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF).
- the metallocene compound includes a metal element-containing compound described later and having a radical polymerization initiation ability.
- the photoradical polymerization initiator is more preferably an oxime compound.
- the exposure latitude can be improved more effectively.
- the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
- the compound described in JP-A-2001-233842 the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.
- Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
- an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator.
- IRGACURE OXE 01 IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052).
- a radical polymerization initiator 2) is also preferably used.
- TR-PBG-304 manufactured by Changshu Powerful Electronics New Materials Co., Ltd.
- ADEKA ARCLUDS NCI-831 ADEKA ARCULDS NCI-930
- DFI-091 manufactured by Daito Chemix Co., Ltd.
- 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. 06636081.
- 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 an oxime compound include the compounds described in International Publication No. 2013/083505.
- an oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.
- Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.
- the photoradical 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.
- 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, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is 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
- 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.
- RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like.
- R I01 is a group represented by formula (II), the same as R I00 It is a group, and R I02 to R I04 are independently alkyl having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.
- R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
- the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/1254669 can also be used.
- 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 composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of 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.
- the composition of the present invention preferably contains a photoacid generator as a photosensitizer.
- a photoacid generator for example, acid is generated in the exposed portion of the composition layer, the solubility of the exposed portion in the developing solution (for example, an alkaline aqueous solution) is increased, and the exposed portion is affected by the developing solution. A positive pattern to be removed can be obtained.
- the composition contains a photoacid generator and a polymerizable compound other than the radically polymerizable compound described later, for example, the acid generated in the exposed portion promotes the cross-linking reaction of the polymerizable compound.
- the exposed portion may be more difficult to be removed by the developing solution than the non-exposed portion. According to such an aspect, a negative type pattern can be obtained.
- the photoacid generator is not particularly limited as long as it generates an acid by exposure, but is an onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime.
- onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime.
- examples thereof include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl sulfonate.
- the quinone diazide compound a polyhydroxy compound in which quinone diazide sulfonic acid is bonded by an ester, a polyamino compound in which quinone diazide sulfonic acid is conjugated with a sulfonamide bond, and a polyhydroxypolyamino compound in which quinone diazide sulfonic acid is ester-bonded and a sulfonamide bond.
- the one which is bound by at least one of the above is mentioned.
- it is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.
- the quinone diazide either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used.
- the 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
- the 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
- a 4-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed.
- a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group may be contained in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound may be contained. It may be contained.
- the naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinone diazido sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.
- Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds of these compounds. Be done.
- Examples of the onium salt compound or the sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.
- the photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as “oxime sulfonate compound”).
- oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-) It is preferably an oxime sulfonate compound represented by 105).
- X 3 is an alkyl group, an alkoxyl group, or a halogen atom. If X 3 there are a plurality, each be the same or may be different. Alkyl group and an alkoxyl group represented by X 3 may have a substituent.
- the halogen atom in the X 3, a chlorine atom or a fluorine atom is preferable.
- m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X 3 may be the same or different.
- R 34 represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxyl group of numbers 1 to 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W or an anthranyl group optionally substituted with W.
- W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxyl halide having 1 to 5 carbon atoms. It represents a group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.
- oxime sulfonate compound represented by the formula (OS-1) are described in paragraphs 0064 to 0068 of JP2011-209692A and paragraph numbers 0158 to 0167 of JP2015-194674A. The following compounds are exemplified and their contents are incorporated herein.
- R s1 represents an alkyl group, an aryl group or a heteroaryl group
- R s6 which represents a group or a halogen atom and may be present in a plurality, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group
- Xs represents O or S.
- ns represents 1 or 2
- ms represents an integer from 0 to 6.
- an alkyl group represented by R s1 preferably having 1 to 30 carbon atoms
- an aryl group preferably having 6 to 30 carbon atoms
- a heteroaryl group carbon
- numbers 4 to 30 may have a substituent T.
- R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms). , Hydrogen atom or alkyl group is more preferable.
- R s2 that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.
- the alkyl group or aryl group represented by R s2 may have a substituent T.
- Xs represents O or S, and is preferably O.
- the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
- ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
- the alkyl group represented by R s6 preferably having 1 to 30 carbon atoms
- the alkyloxy group preferably having 1 to 30 carbon atoms
- ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.
- the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111).
- the compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS-105). -108) or a compound represented by the formula (OS-109) is particularly preferable.
- R t1 represents an alkyl group, an aryl group or a heteroaryl group
- R t7 represents a hydrogen atom or a bromine atom
- R t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups
- R t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups
- R t2 represents a hydrogen atom or a methyl group.
- R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
- R t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, or a phenyl group.
- it represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. It is more preferable to have a methyl group, and it is particularly preferable to have a methyl group.
- R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
- R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
- the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
- Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692A and paragraphs of JP2015-194674A.
- the compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.
- oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
- Ru9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Represents an aryl group or a heteroaryl group.
- R u9 is a cyano group or an aryl group is more preferable, and the embodiment in which R u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
- Ru2a represents an alkyl or aryl group.
- Xu is -O-, -S-, -NH- , -NR u5-, -CH 2- , -CR u6 H- or CR u6 R u7.
- Ru1 to Ru4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxyl group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group. 2 in turn, each may be bonded to each other to form a ring of the R u1 ⁇ R u4. At this time, the ring may be condensed to form a condensed ring together with the benzene ring.
- R u1 ⁇ R u4 a hydrogen atom, preferably a halogen atom or an alkyl group, also aspects to form the at least two aryl groups bonded to each other of R u1 ⁇ R u4 preferred.
- Ru1 to Ru4 are hydrogen atoms. Any of the above-mentioned substituents may further have a substituent.
- the compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
- the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
- Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraph numbers 0102 to 0106 of JP2011-209692 and paragraph numbers 0195 to 0207 of JP2015-194674. These contents are incorporated herein by reference.
- b-9, b-16, b-31, and b-33 are preferable.
- a commercially available product may be used as the photoacid generator.
- Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-376, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-69 (any of which).
- Fujifilm Wako Pure Chemical Industries, Ltd. Omnicat 250, Omnicat 270 (all manufactured by IGM Resins BV), Irgacure 250, Irgacure 270, Irgacure 290 (all manufactured by BASF), MBZ-101 (all manufactured by BASF) (Made by Midori Chemical Industries, Ltd.) and the like.
- an organic halogenated compound can also be applied.
- the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-46-4605, JP-A. 48-36281, JP-A-55-3270, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62- 212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, M.D. P.
- an s-triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is attached to the s-triazine ring specifically, for example 2,4,6-tris (monochromomethyl)- s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- ( ⁇ , ⁇ , ⁇ -trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine , 2-Phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (
- an organic borate compound can also be applied.
- the organic borate compound include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, and JP-A-2000. -131837, JP-A-2002-107916, Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin "Rad Tech '98. Proceeding April 19-22, 1998, Chicago" and the like.
- Specific examples thereof include organic boron transition metal coordination complexes of JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014.
- a disulfone compound can also be applied as a photoacid generator.
- examples of the disulfone compound include compounds described in JP-A-61-166544, Japanese Patent Application Laid-Open No. 2001-132318, and diazodisulfone compounds.
- onium salt compound examples include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18,387 (1974), T.K. S. The diazonium salt described in Bal et al, Polymer, 21,423 (1980), the ammonium salt described in US Pat. No. 4,069,055, JP-A-4-365549, etc., US Pat. No. 4,069, Phosphonium salts described in 055, 4,069,056, European Patents 104, 143, US Patents 339,049, 410,201, JP-A-2. -150848, Iodonium salt described in JP-A-2-296514, European Patent Nos.
- onium salts examples include onium salts represented by the following general formulas (RI-I) to (RI-III).
- Ar 11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 1 carbon atom.
- Z11 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, surface stability
- Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion are preferable.
- Ar 21 and Ar 22 each represent an aryl group having 20 or less carbon atoms which may independently have 1 to 6 substituents, and preferred substituents have 1 to 12 carbon atoms.
- Z 21 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, From the viewpoint of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
- R 31 , R 32 , and R 33 each represent an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 20 or less carbon atoms which may independently have 1 to 6 substituents.
- an aryl group from the viewpoint of reactivity and stability.
- Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms.
- Examples thereof include a group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms.
- Z31 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of properties, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
- 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 composition of the present invention. It is more preferably 2 to 15% by mass. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more photoacid generators are contained, the total is preferably in the above range.
- the curable resin composition of the present invention contains 1 to 40 parts by mass of the photosensitive agent and 0. It is preferable to contain 05 to 20 parts by mass and 50 to 300 parts by mass of the above-mentioned solvent.
- the content of the photosensitizer is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 2 to 10 parts by mass with respect to 100 parts by mass of the specific resin.
- the content of the specific compound is preferably 0.1 to 15 parts by mass, more preferably 0.2 to 10 parts by mass, and 0.5 to 8 parts by mass with respect to 100 parts by mass of the specific resin. Is particularly preferable.
- the content of the solvent is preferably 70 to 250 parts by mass, more preferably 80 to 230 parts by mass, and particularly preferably 100 to 200 parts by mass with respect to 100 parts by mass of the specific resin.
- the composition of the present invention may contain a thermal polymerization initiator, and in particular, a thermal radical polymerization initiator.
- a thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be allowed to proceed in the heating step described later, so that the solvent resistance can be further improved.
- thermal radical polymerization initiator examples include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
- 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 composition of the present invention. More preferably, it is 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 composition of the present invention may contain a thermoacid generator.
- the thermoacid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound. It has the effect of making it.
- the thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the composition is applied to the substrate, and during final heating (cure: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
- the thermal decomposition start temperature is obtained as the peak temperature of the exothermic peak, which is the lowest temperature when the thermoacid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule. Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).
- the acid generated from the thermoacid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane.
- aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid
- alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid
- haloalkyl sulfonic acid such as sulfonic acid is preferable.
- thermoacid generator include those described in paragraph 0055 of JP2013-072935A.
- thermoacid generator the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermoacid generator.
- the content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin.
- the content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin.
- 0.01 part by mass or more By containing 0.01 part by mass or more, the cross-linking reaction is promoted, so that the mechanical properties and solvent resistance of the organic film can be further improved.
- 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is further preferable.
- the curable resin composition of the present invention may further contain an onium salt.
- the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it preferably contains an onium salt.
- the type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt and phosphonium salt are preferably mentioned.
- an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability
- a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.
- the onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bonded via a covalent bond. .. That is, the onium salt may be an intramolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are separate molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the curable resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
- an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.
- the onium salt used in the present invention may be a thermobase generator described later.
- the thermal base generator refers to a compound that generates a base by heating, and examples thereof include a compound that generates a base when heated to 40 ° C. or higher.
- ammonium salt means a salt of an ammonium cation and an anion.
- R 1 to R 4 each independently represent a hydrogen atom or a hydrocarbon group, and at least two of R 1 to R 4 may be bonded to each other to form a ring.
- R 1 to R 4 are each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms or 6 to 6 carbon atoms. It is more preferably 12 aryl groups.
- R 1 to R 4 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy. Examples thereof include a carbonyl group and an acyloxy group.
- the ring may contain a hetero atom. Examples of the hetero atom include a nitrogen atom.
- the ammonium cation is preferably represented by any of the following formulas (Y1-1) and (Y1-2).
- R 101 represents an n-valent organic group
- R 1 has the same meaning as R 1 in the formula (101)
- Ar 101 and Ar 102 are each independently , Represents an aryl group
- n represents an integer of 1 or more.
- R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
- n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
- Ar 101 and Ar 102 are preferably phenyl groups or naphthyl groups, respectively, and more preferably phenyl groups.
- the anion in the ammonium salt one selected from a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfuric acid anion is preferable, and a carboxylic acid anion is more preferable because both salt stability and thermodegradability can be achieved.
- the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
- the carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxy groups, and more preferably a divalent carboxylic acid anion.
- the stability, curability and developability of the curable resin composition can be further improved.
- the stability, curability and developability of the curable resin composition can be further improved.
- the carboxylic acid anion is preferably represented by the following formula (X1).
- EWG represents an electron-attracting group.
- the electron-attracting group means that Hammett's substituent constant ⁇ m shows a positive value.
- ⁇ m is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642.
- the EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
- R x1 to R x3 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group or a carboxy group, and Ar is an aromatic group. Represents.
- the carboxylic acid anion is preferably represented by the following formula (XA).
- L 10 represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR X - represents and divalent connecting group selected from the group consisting a combination thereof, R X is , Hydrogen atom, alkyl group, alkenyl group or aryl group.
- carboxylic acid anion examples include maleic acid anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion.
- the onium salt in the present invention contains an ammonium cation as a cation from the viewpoint that the cyclization of the heterocyclic polymer-containing precursor is easily performed at a low temperature and the storage stability of the curable resin composition is easily improved.
- the salt as an anion, it is preferable to contain an anion having a conjugate acid pKa (pKaH) of 2.5 or less, and more preferably to contain an anion having a pKa (pKaH) of 1.8 or less.
- the lower limit of pKa is not particularly limited, but it is preferably -3 or more, preferably -2 or more, from the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of the heterocyclic polymer-containing precursor or the like is improved.
- the above is more preferable.
- the above pKa includes Determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O., Nachod, F.C.; See Nachod, F.C .; Academic Press, New York, 1955) and Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 19). Can be done. For compounds not described in these documents, the values calculated from the structural formulas using software of ACD / pKa (manufactured by ACD / Labs) shall be used.
- ammonium salt examples include the following compounds, but the present invention is not limited thereto.
- the iminium salt means a salt of an iminium cation and an anion.
- the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
- a pyridinium cation is preferable.
- a cation represented by the following formula (102) is also preferable.
- R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group
- R 7 represents a hydrocarbon group
- at least two of R 5 to R 7 are bonded to each other to form a ring. It may be formed.
- R 5 and R 6 are synonymous with R 1 to R 4 in the above formula (101), and the preferred embodiment is also the same.
- R 7 preferably combines with at least one of R 5 and R 6 to form a ring.
- the ring may contain a heteroatom. Examples of the hetero atom include a nitrogen atom. Further, as the ring, a pyridine ring is preferable.
- the iminium cation is preferably represented by any of the following formulas (Y1-3) to (Y1-5).
- R 101 represents an n-valent organic group
- R 5 has the same meaning as R 5 in the formula (102)
- R 7 is R in the formula (102) Synonymous with 7
- n and m represent integers of 1 or more.
- R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the structure to which these are bonded, and has 2 to 30 carbon atoms.
- n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
- m is preferably 0 to 4, more preferably 1 or 2, and even more preferably 1.
- iminium salt examples include the following compounds, but the present invention is not limited thereto.
- the sulfonium salt means a salt of a sulfonium cation and an anion.
- the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
- sulfonium cation a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable. Further, as the sulfonium cation, a cation represented by the following formula (103) is preferable.
- R 8 to R 10 each independently represent a hydrocarbon group.
- R 8 to R 10 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
- R 8 to R 10 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy.
- the substituent preferably has an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and has a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 1 to carbon atoms. It is more preferable to have 10 alkoxy groups.
- R 8 to R 10 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
- sulfonium salt examples include the following compounds, but the present invention is not limited thereto.
- the iodonium salt means a salt of an iodonium cation and an anion.
- the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
- iodonium cation a diaryl iodonium cation is preferable. Further, as the iodonium cation, a cation represented by the following formula (104) is preferable.
- R 11 and R 12 each independently represent a hydrocarbon group.
- R 11 and R 12 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
- R 11 and R 12 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy.
- Examples thereof include a carbonyl group and an acyloxy group.
- R 11 and R 12 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
- iodonium salt examples include the following compounds, but the present invention is not limited thereto.
- the phosphonium salt means a salt of a phosphonium cation and an anion.
- the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
- a quaternary phosphonium cation is preferable, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation. Further, as the phosphonium cation, a cation represented by the following formula (105) is preferable.
- R 13 to R 16 each independently represent a hydrogen atom or a hydrocarbon group.
- R 13 to R 16 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
- R 13 to R 16 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy.
- Examples thereof include a carbonyl group and an acyloxy group.
- R 13 to R 16 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
- phosphonium salt examples include the following compounds, but the present invention is not limited thereto.
- the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention.
- the lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more.
- the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
- the onium salt one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
- the curable resin composition of the present invention may further contain a thermosetting agent.
- a thermosetting agent when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to contain a thermosetting agent.
- the other thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
- Examples of the thermobase generator other than the above-mentioned onium salt include nonionic thermobase generators. Examples of the nonionic thermobase generator include compounds represented by the formula (B1) or the formula (B2).
- 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 fused ring in which two monocyclic rings or two monocyclic rings are condensed is preferable.
- the single ring is preferably a 5-membered ring or a 6-membered ring, and 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 to 18 are more preferred, 3 to 12 are more preferred), aryl groups (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, 6 to 10 are more preferred), or arylalkyl groups (7 carbon atoms are more preferred). ⁇ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have substituents as long as the effects of the present invention are exhibited.
- Rb 1 and Rb 2 may be coupled to each other to form a ring.
- a 4- to 7-membered nitrogen-containing heterocycle is preferable.
- Rb 1 and Rb 2 are particularly linear, branched, or cyclic alkyl groups that may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12). 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.
- a cyclohexyl group which may be used is more preferable.
- 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.
- alkoxy group (2 to 24 carbon atoms are preferable, 2 to 12 is more preferable, 2 to 6 is more preferable
- arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable).
- an arylalkenyl group (8 to 24 carbon atoms is preferable, 8 to 20 is more preferable, 8 to 16 is more preferable), and an alkoxyl group (1 to 24 carbon atoms is preferable, 2 to 2 to 24).
- 18 is more preferable, 3 to 12 is more preferable), an aryloxy group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), or an arylalkyloxy group (7 to 12 carbon atoms is more preferable).
- 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is further preferable).
- a cycloalkyl group (preferably having 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. Of these, 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). , 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), arylalkyl groups (7 to 7 to carbon atoms are more preferable). 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is further preferable), and a hydrogen atom is preferable.
- Rb 35 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), 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), aryl group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable). , 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 have the same meanings as 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, further 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, further preferably 6 to 10 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, 7).
- Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), 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), 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.
- the molecular weight of the nonionic thermobase 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.
- thermo base generators or specific examples of thermal base generators other than the above-mentioned onium salts include the following compounds.
- the content of the other thermobase generator is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
- the thermobase generator one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
- the curable resin composition of the present invention preferably contains a cross-linking agent.
- the cross-linking agent include radical cross-linking agents and other cross-linking agents.
- the curable resin composition of the present invention preferably further contains a radical cross-linking agent.
- the radical cross-linking agent is a compound having a radically polymerizable group.
- a group containing an ethylenically unsaturated bond is preferable.
- the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
- the (meth) acryloyl group is preferable as the group containing the ethylenically unsaturated bond, and the (meth) acryloyl group is more preferable from the viewpoint of reactivity.
- the radical cross-linking agent may be a compound having one or more ethylenically unsaturated bonds, but is more preferably a compound having two or more ethylenically unsaturated bonds.
- the compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above ethylenically unsaturated bonds.
- the curable resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical cross-linking agent.
- the compound having 3 or more ethylenically unsaturated bonds a compound having 3 to 15 ethylenically unsaturated bonds is preferable, and a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and 3 to 6 compounds are more preferable.
- the compound having is more preferable.
- the compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bond, and more preferably a compound having 3 to 15 ethylenically unsaturated bonds.
- a compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
- the curable resin composition of the present invention has a compound having two ethylenically unsaturated bonds and three or more ethylenically unsaturated bonds. It is also preferable to include a compound.
- 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, which are preferably unsaturated.
- an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group.
- a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
- an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, thiols, and a halogeno group is 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.
- a compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993.
- Urethane (meth) acrylates such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.
- a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
- 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.
- dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues. A structure that is bonded together is preferable
- SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
- SR-209 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 Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765.
- Urethane compounds having an ethylene oxide-based structure 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 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.
- a radical cross-linking agent provided with is more preferable.
- the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound.
- examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
- the preferable acid value of the radical cross-linking agent having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
- the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizable property is good.
- the acid value 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 is measured according to the description of JIS K 0070: 1992.
- bifunctional metal acrylate 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, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, and polytetraethylene.
- Glycol diacrylate polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol Dimethacrylate, dimethylol-tricyclodecanediacrylate, dimethylol-tricyclodecanedimethacrylate, EO adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, PO of bisphenol A Additives Dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates
- 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.
- 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.
- (meth) Acrylic acid derivatives N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate 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 content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable 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.
- One type of radical cross-linking agent may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.
- the curable resin composition of the present invention preferably contains another cross-linking agent different from the radical cross-linking agent described above.
- the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and a covalent bond is formed with another compound in the composition or a reaction product thereof by exposure to the above-mentioned photosensitizer.
- the compound has a plurality of groups in the molecule for which the reaction to be formed is promoted, and the reaction of forming a covalent bond with another compound in the composition or a reaction product thereof is the action of an acid or a base.
- a compound having a plurality of groups promoted by the above in the molecule is preferable.
- the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator, which is a photosensitizer, in an exposure step such as a first region exposure step or a second region exposure step.
- a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is a nitrogen atom.
- a compound having a structure directly bonded to 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 a methylol group or an alkoxymethyl group.
- examples thereof include compounds having a substituted structure.
- the method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
- 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 curable 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 preferably contains a glycoluril-based cross-linking agent and melamine, which will be described later. It is more preferable to contain at least one compound selected from the group consisting of system cross-linking agents.
- melamine-based cross-linking agent examples include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutyl melamine and the like.
- urea-based cross-linking agent examples include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol uryl.
- Glycoluryl-based cross-linking agent such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, Monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethyl
- Ethyleneurea-based cross-linking agents such as ethyleneurea, monobutoxymethylated, or dibutoxymethylated ethyleneurea, Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethyl
- benzoguanamine-based cross-linking agent examples include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
- Tetramethoxymethylated benzoguanamine Tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxy Methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like can be mentioned.
- a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
- a compound to which a group is directly bonded is also preferably used.
- Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylbenzoate hydroxymethylphenyl.
- 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.
- DML-34X DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, Honshu) Nikalac (registered trademark, the same applies
- the curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.
- Epoxy compound (compound having an epoxy group)
- the epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Since 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, film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the curable resin composition.
- the epoxy compound preferably contains a polyethylene oxide group.
- the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
- epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether.
- Examples of the contained silicone and the like can be mentioned, but the present invention is not limited to these.
- oxetane compound compound having an oxetanyl group
- examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, and the like.
- examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like.
- the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone. Alternatively, two or more types may be mixed.
- Benzoxazine compound (compound having a benzoxazolyl group) Since the benzoxazine compound is a cross-linking reaction derived from the cycloaddition reaction, degassing does not occur during curing, and the heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.
- benzoxazine compound are BA type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, FA type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), poly.
- examples thereof include a benzoxazine adduct of a hydroxystyrene resin and a phenol novolac type dihydrobenzoxazine compound. 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, based on the total solid content of the curable resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass.
- the other cross-linking agent may contain only one type, or may contain two or more types. When two or more other cross-linking agents are contained, the total is preferably in the above range.
- the curable 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 curable resin composition layer.
- the above-mentioned compound having a triazole structure does not correspond to a migration inhibitor.
- the migration inhibitor is not particularly limited, but a heterocycle (pyran ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
- tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.
- an ion trap agent that traps anions such as halogen ions can also be used.
- Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656.
- the compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used.
- the migration inhibitor include the following compounds.
- the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the curable resin composition, and is 0. It is more preferably 0.05 to 2.0% by mass, and further preferably 0.1 to 1.0% by mass.
- the migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably in the above range.
- the curable resin composition of the present invention preferably contains a polymerization inhibitor.
- polymerization inhibitor examples include hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, and diphenyl-p-benzoquinone.
- the content of the polymerization inhibitor is 0.01 to 20.0% by mass based on the total solid content of the curable resin composition of the present invention. It is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and further preferably 0.05 to 2.5% by mass.
- the polymerization inhibitor may be only one type or two or more types. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
- the curable 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 silane coupling agents, aluminum-based adhesive aids, titanium-based adhesive aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, ⁇ -ketoester compounds, amino compounds and the like. And so on.
- silane coupling agent examples include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992.
- Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent.
- Et represents an ethyl group.
- silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid.
- Aluminum-based adhesive aid examples include aluminum tris (ethylacetacetate), aluminumtris (acetylacetoneate), ethylacetacetate aluminum diisopropirate, and the like.
- the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used.
- the content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further, with respect to 100 parts by mass of the heterocyclic polymer precursor. It is preferably in the range of 0.5 to 5 parts by mass.
- the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.
- the curable resin composition of the present invention contains various additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, and inorganic particles, if necessary, as long as the effects of the present invention can be obtained.
- additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, and inorganic particles, if necessary, as long as the effects of the present invention can be obtained.
- Curing agent, curing catalyst, filler, antioxidant, ultraviolet absorber, anti-aggregation agent and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.
- the curable resin composition of the present invention may contain a sensitizer.
- the sensitizer absorbs specific active radiation and becomes an electron-excited state.
- the sensitizer in the electronically excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur.
- the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases.
- a sensitizing dye may be used as the sensitizer.
- the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.
- the content of the sensitizer may be 0.01 to 20% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass.
- the sensitizer may be used alone or in combination of two or more.
- the curable 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.
- As the chain transfer agent for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
- a thiol compound can be preferably used.
- the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition of the present invention.
- 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable.
- the chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.
- Each type of surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving the coatability.
- the surfactant various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used.
- the following surfactants are also preferable.
- the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit
- the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.
- the surfactant the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
- 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 include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP2010-164965, such as Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. Can be mentioned.
- 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 of coating film thickness and liquid saving property, 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 Co., Ltd.), KP341, KF6001, KF6002 (manufactured by Shin-Etsu 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 propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc.
- organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
- (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 77, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.
- W001 manufactured by Yusho Co., Ltd.
- anionic 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 0.001 to 2.0% by mass based on the total solid content of the curable resin composition of the present invention. It is preferably 0.005 to 1.0% by mass, more preferably 0.005 to 1.0% by mass.
- the surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total is preferably in the above range.
- the curable resin composition of the present invention has a curable resin composition in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of an object.
- a higher fatty acid derivative such as behenic acid or behenic acid amide
- the content of the higher fatty acid derivative is 0.1 to 10% by mass based on the total solid content of the curable resin composition of the present invention. Is preferable.
- 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 in particular, a thermal radical polymerization initiator.
- a 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 allowed to proceed by adding the thermal radical polymerization initiator, the solvent resistance can be further improved.
- thermal radical polymerization initiator examples include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
- 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 mechanical properties of the cured film may deteriorate.
- the average particle size of the inorganic particles exceeds 2.0 ⁇ m, the resolution may decrease due to scattering of exposure light.
- 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 ultraviolet absorbers examples include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and examples of benzophenone-based ultraviolet 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- Hydroxy-4-octoxybenzophenone and the like can be mentioned.
- benzotriazole-based ultraviolet absorbers examples include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3). '-Tert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2-( 2'-Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [
- 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. Furthermore, examples of triazine-based ultraviolet absorbers include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl).
- 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 negative photosensitive resin composition has good storage stability and a good curing pattern can be obtained.
- Specific examples are titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanionate, titanium diisopropoxyside bis (2,4-pentanionate)).
- Titanium diisopropoxyside bis tetramethylheptandionate
- titanium diisopropoxyside bis ethylacetacetate
- Tetraalkoxytitanium 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 Butokiside ⁇ ] etc.
- Titanosen 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.
- VI) Titanium tetraacetylacetone compound For example, titanium tetraacetylacetone.
- Titanate Coupling Agent For example, isopropyltridodecylbenzenesulfonyl titanate 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) titanosen 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 precursor of the cyclized resin. ..
- the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition is 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.
- a phosphorus-based antioxidant tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6 -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like.
- 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, 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.
- 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. As a result, a compound in which the protecting group is eliminated and functions as an antioxidant can be mentioned.
- Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
- Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like.
- preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds represented by the general formula (3).
- R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms
- R 6 represents an alkylene group having 2 or more carbon atoms
- R 7 represents a 1- to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom
- k represents an integer of 1 to 4.
- the compound represented by the general formula (3) suppresses oxidative deterioration of aliphatic groups and phenolic hydroxyl groups of the resin.
- metal oxidation can be suppressed by the rust preventive action on the metal material.
- R7 includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a 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 and -NH- from the viewpoint of solubility in a developing solution and metal adhesion, and -NH- is more preferable from the viewpoint of metal adhesion due to interaction with resin and metal complex formation. preferable.
- Examples of the compound represented by the following 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. If the amount added is less than 0.1 parts by mass, it is difficult to obtain the effect of improving the elongation characteristics after reliability and the adhesion to the metal material, and if it is more than 10 parts by mass, it is due to the interaction with the photosensitizer. , There is a risk of lowering the sensitivity of the resin composition. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
- the water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties.
- Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container.
- the metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulating properties.
- the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range.
- a raw material having a low metal content is selected as a raw material constituting the curable resin composition of the present invention.
- Methods such as filtering the raw materials constituting the curable resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible can be mentioned. be able to.
- the curable 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 more preferably 200 mass ppm from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. 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 curable resin composition of the present invention.
- a multi-layer bottle having the inner wall of the container composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a layered bottle. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
- the curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer. In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.
- the curable 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.
- the filter pore diameter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less. On the other hand, from the viewpoint of productivity, 5 ⁇ m or less is preferable, 3 ⁇ m or less is more preferable, and 1 ⁇ m or less is further preferable.
- the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
- 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.
- filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, 0.01 MPa or more and 1.0 MPa or less is preferable, 0.03 MPa or more and 0.9 MPa or less is more preferable, and 0.05 MPa or more and 0.7 MPa or less is further preferable. In addition to filtration using a filter, impurities may be removed using an adsorbent.
- Filter filtration and impurity removal treatment using an adsorbent may be combined.
- a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
- the cured film of the present invention is obtained by curing the curable resin composition of the present invention.
- the film thickness of the cured film of the present invention can be, for example, 0.5 ⁇ m or more, and can be 1 ⁇ m or more. Further, the upper limit value can be 100 ⁇ m or less, and can be 30 ⁇ m or less.
- the cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. It is preferable that the laminate of the present invention contains two or more cured films and includes a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferable.
- the first cured film and the second cured film are both cured films of the present invention.
- both the first cured film and the second cured film are curable of the present invention.
- a preferred embodiment is a film obtained by curing the resin composition.
- the curable resin composition of the present invention used for forming the first cured film and the curable resin composition of the present invention used for forming the second cured film have the same composition. It may be present, or it may be a composition having a different composition.
- the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
- Examples of applicable fields of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
- Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above.
- the cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially in microelectronics.
- the method for producing a cured film of the present invention includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film.
- the method for producing a cured film of the present invention preferably includes the film forming step, an exposure step for exposing the film, and a developing step for developing the film.
- the method for producing a cured film of the present invention more preferably includes the film forming step and, if necessary, the developing step, and also includes a heating step of heating the film at 50 to 450 ° C. Specifically, it is also preferable to include the following steps (a) to (d).
- A Film forming step of applying the curable resin composition to a substrate to form a film (curable resin composition layer)
- Exposure step of exposing the film after the film forming step (c) Exposure Development step for developing the above-mentioned film
- the method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention.
- the method for producing the laminated body of the present embodiment is the step (a), the steps (a) to (c), or (a) after forming the cured film according to the above-mentioned method for producing the cured film. )-(D).
- a laminated body can be obtained.
- the production method includes a film forming step (layer forming step) in which the curable resin composition is applied to a substrate to form a film (layered).
- the type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, There are no particular restrictions on magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like. Further, these base materials may be provided with a layer such as an adhesion layer or an oxide layer on the surface thereof. In the present invention, 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.
- 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.
- a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
- HMDS hexamethyldisilazane
- the base material for example, a plate-shaped base material (board) is used.
- the shape of the base material is not particularly limited, and may be circular or rectangular, but is preferably 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.
- the resin layer or the metal layer serves as a base material.
- Coating is preferable as a means for applying the curable resin composition to the base material.
- the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method.
- the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable.
- a resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the base material.
- a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular base material, a slit coating method or a spray coating method is preferable.
- the method, the inkjet method and the like are preferable.
- the spin coating method for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. Further, depending on the viscosity of the photosensitive resin composition and the film thickness to be set, it is preferable to apply the photosensitive resin composition at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds.
- a plurality of rotation speeds can be combined and applied. Further, it is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate. Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention. Further, a step of removing the excess film at the edge of the base material may be performed. Examples of such a process include edge bead rinse (EBR), air knife, back rinse and the like. Further, a pre-wetting 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.
- EBR edge bead rinse
- the production method of the present invention may include a step of forming the film (curable resin composition layer), followed by a film forming step (layer forming step), and then drying to remove the solvent.
- the preferred drying temperature is 50 to 150 ° C., more preferably 70 ° C. to 130 ° C., still more preferably 90 ° C. to 110 ° C.
- the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
- the production method of the present invention may include an exposure step of exposing the film (curable resin composition layer).
- the amount of exposure is not particularly determined as long as the curable resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ /. It is more preferable to irradiate with cm 2.
- the exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
- the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h.
- the curable 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.
- a broad (three wavelengths of g, h, and i rays) light source of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.
- the production method of the present invention may include a developing step of developing the exposed film (curable resin composition layer) (developing the film). By developing, the unexposed portion (non-exposed portion) is removed.
- the developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection of a developing solution from a nozzle, spray spraying, immersion of a developing solution in a base material, and the like, and ejection from a nozzle is preferably used.
- the developing process includes a process in which the developing solution is continuously supplied to the base material, a step in which the developing solution is kept in a substantially stationary state on the base material, a step in which the developing solution is vibrated by ultrasonic waves or the like, and a combination thereof. Processes can be adopted.
- Development is carried out using a developing solution.
- the developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
- As the developing solution a developing solution containing an organic solvent or an alkaline aqueous solution can be used.
- the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3.
- the ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
- the organic solvent may be, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate.
- alkyl alkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate) , Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.
- 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) , 3-Methylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)
- the developer is a developer containing an organic solvent
- cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable in the present invention.
- the developing solution contains an organic solvent, one kind or a mixture of two or more kinds of organic solvents can be used.
- the developer is a developer containing an organic solvent
- 50% by mass or more of the developer is preferably an organic solvent
- 70% by mass or more is more preferably an organic solvent
- 90% by mass or more is organic. It is more preferably a solvent.
- the developing solution may be 100% by mass of an organic solvent.
- the developer may further contain other components.
- other components include known surfactants and known defoamers.
- the developing solution is an alkaline aqueous solution
- examples of the basic compound that the alkaline aqueous solution can contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate and the like, and TMAH is preferable. ..
- TMAH tetramethylammonium hydroxide
- KOH potassium hydroxide
- sodium carbonate sodium carbonate
- TMAH is preferable.
- the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3% by mass in the total mass of the developer. Is more preferable.
- the method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the developer, the method of supplying the developer on the base material using a nozzle, paddle development, or continuous development. There is a way to supply.
- the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoint of the permeability of the developer, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developer with a straight nozzle or the method of continuously supplying the developer with a spray nozzle is preferable, and the developer is supplied to the image area.
- 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, and this step may be repeated a plurality of times. Further, as a method of supplying the developer in the developing process, a step in which the developer is continuously supplied to the base material, a step in which the developer is kept in a substantially stationary state on the base material, and a step in which the developer is superposed 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 development time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes.
- the temperature of the developing solution at the time of development is not particularly specified, but it can be usually 10 to 45 ° C, preferably 20 to 40 ° C.
- rinsing After the treatment with the developing solution, further rinsing may be performed. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
- the rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with a solvent contained in the curable resin composition.
- the rinse solution include PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), and the like, preferably PGMEA.
- water is preferable as the rinsing solution for development with a developing solution containing an alkaline aqueous solution.
- the rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, still more preferably 5 seconds to 1 minute.
- the temperature of the rinsing liquid at the time of rinsing is not particularly specified, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
- Examples of the organic solvent when the rinsing solution contains an organic solvent include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate.
- alkyl alkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid) E
- toluene, xylene, anisole, limonene, etc. dimethyl sulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene as alcohols.
- glycols and the like and amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.
- 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 and PGME are particularly preferable, cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, PGMEA and 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 defoamers.
- the method of supplying the rinse liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinse liquid, the paddle development on the base material, the method of supplying the rinse liquid to the base material by a shower, and the base material.
- the method of supplying the rinse liquid 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. That is, 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 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 conditioner or the like and a process of combining them can be adopted.
- the production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ° C.
- the heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step.
- the above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the precursor, which is a specific resin, proceeds.
- the curable resin composition of the present invention may contain a radically polymerizable compound other than the precursor which is a specific resin, but may also cure a radically polymerizable compound other than the precursor which is an unreacted specific resin. It can be advanced in this step.
- the heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable.
- the upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.
- the heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
- a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
- the temperature at the start of heating 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 temperature of the film (layer) after drying is higher than, for example, the boiling point of the solvent contained in the curable resin composition. It is preferable to gradually raise the temperature from a temperature as low as 30 to 200 ° C.
- the heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.
- the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the specific resin between the layers are undergoing a cross-linking reaction at this temperature.
- Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed.
- the heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547.
- the pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
- the pretreatment may be performed in two or more steps.
- the pretreatment step 1 may be performed in the range of 100 to 150 ° C.
- the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
- cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
- the heating step is performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the specific resin.
- the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
- the heating means is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, and a hot air oven.
- the production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (curable resin composition layer).
- metal layer existing metal types can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, and copper, aluminum, and these metals are exemplified.
- the alloy containing the above is more preferable, and copper is further preferable.
- the method for forming the metal layer is not particularly limited, and an existing method can be applied.
- the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used.
- photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
- the thickness of the metal layer is preferably 0.01 to 100 ⁇ m, more preferably 0.1 to 50 ⁇ m, and even more preferably 1 to 10 ⁇ m at the thickest portion.
- the production method of the present invention preferably further includes a laminating step.
- the laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step are performed again on the surface of the cured film (resin layer) or the metal layer. , A series of steps including performing in this order. However, the mode may be such that only the film forming step (a) is repeated. Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated curable resin composition layers all at once.
- the (c) developing step may be followed by the (e) metal layer forming step, and even if the heating is performed each time (d), the (d) is collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step, and the like as appropriate.
- the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step.
- An example of the surface activation treatment is plasma treatment.
- the laminating step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times. Further, each layer in the laminating step may be a layer having the same composition, shape, film thickness, etc., or may be a different layer.
- the resin layer is 2 or more and 20 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and a configuration of 3 or more and 7 or less is more preferable. More preferably, it has 3 or more layers and 5 or less layers.
- a cured film (resin layer) of the curable resin composition so as to cover the metal layer after the metal layer is provided.
- Examples thereof include an embodiment in which (b) an exposure step, (c) a development step, and (e) a metal layer forming step are repeated in this order, and (d) a heating step is collectively provided at the end or in the middle.
- the method for producing a laminate of the present invention may include a surface activation treatment step of surface activating at least a part of the metal layer and the photosensitive resin composition layer.
- the surface activating treatment step is usually performed after the metal layer forming step, but it is also possible to perform the surface activating treatment step on the photosensitive resin composition layer after the exposure development step and then perform the metal layer forming step. Good.
- the surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the photosensitive resin composition layer after exposure, or on the metal layer and the photosensitive resin after exposure. For both of the composition layers, each may be at least partially.
- 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 in which the photosensitive resin composition layer is formed on the surface. ..
- the surface activation treatment is performed on a part or all of the photosensitive resin composition layer (resin layer) after exposure.
- the surface activation treatment includes plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, CF 4 / O 2 , NF 3 / O 2 , SF 6 , NF 3 , NF 3 / O 2 , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, then amino group and thiol group It is selected from a dipping treatment in an organic surface treatment agent containing at least one compound and a mechanical roughening treatment using a brush, and a plasma treatment is preferable, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferable.
- the energy is preferably 500 ⁇ 200,000J / m 2, more preferably 1000 ⁇ 100,000J / m 2, and most preferably 10,000 ⁇ 50,000J / m 2.
- the present invention also discloses a semiconductor device containing the cured film or laminate of the present invention.
- the semiconductor device in which the curable 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 the description in FIG. 1 of JP-A-2016-0273557 are taken into consideration. Yes, these contents are incorporated herein.
- the obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate composed of a crude polymer.
- the produced crude polymer was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution.
- the obtained crude polymer solution was added dropwise to 28 liters of water to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer A-1.
- Mw weight average molecular weight
- reaction mixture was then cooled to ⁇ 10 ° C. and 16.12 g (135.5 mmol) of SOCL 2 was added over 10 minutes while keeping the temperature at ⁇ 10 ⁇ 4 ° C. Viscosity increased while SOCL 2 was added.
- the reaction mixture was stirred at room temperature for 2 hours.
- a solution prepared by dissolving 11.75 g (58.7 mmol) of 4,4′-diaminodiphenyl ether in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred at room temperature overnight.
- the polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5000 rpm for 15 minutes.
- the polyimide precursor was collected by filtration, put into 4 liters of water again, stirred for another 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at 45 ° C. for 3 days to obtain polymer A-2.
- Synthesis of Polymer B-2> In Synthesis Example 3, 19.0 g (64.5 mmol) of 3,3'4,4'-biphenyltetra instead of 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride The reaction was carried out in the same manner as described in Synthesis Example 3 except that the carboxylic dianhydride was used to obtain polymer B-2.
- the separable flask was cooled in a water bath at 15 to 20 ° C.
- the time required for dropping was 40 minutes, and the reaction liquid temperature was 30 ° C. at the maximum.
- 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction solution, and the mixture was left to stir for 15 hours at room temperature to remove 99% of all amine terminal groups of the polymer chain. It was sealed with a carboxycyclohexylamide group.
- the reaction rate at this time can be easily calculated by tracking the remaining amount of the charged 1,2-cyclohexyldicarboxylic acid anhydride by high performance liquid chromatography (HPLC).
- Examples and Comparative Examples> In each Example or Comparative Example, among the components shown in Tables 2 to 8 below, components other than the basic compound were mixed to obtain a curable resin composition or a comparative composition.
- the numerical values in the columns of each component other than the solvent shown in Tables 2 to 8 represent the content (parts by mass) of each component.
- the numerical value in the solvent column represents the content (parts by mass) of the solvent used.
- the obtained curable resin composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 ⁇ m. Further, in Tables 2 to 8, the description of "-" indicates that the composition does not contain the corresponding component.
- ⁇ resin ⁇ -A-1, B-1, A-2, B-2, C to F Polymer A-1, polymer B-1, polymer A-2, polymer B-2, polymer C synthesized in the above synthesis example. ⁇ F
- G-6: 1,2,4-triazole (pKa 14.8 in DMSO)
- G-7, G-8 and G-9 are compounds having no triazole
- L-1 A compound represented by the following formula (L-1)
- N-1 to N-3 Compounds having a structure represented by the following formulas (N-1) to (N-3).
- each curable resin composition or each comparative composition was applied (coated) in layers on a copper substrate by a spin coating method to form a curable resin composition layer. ..
- the copper substrate to which the obtained composition layer was applied was dried on a hot plate at 100 ° C. for 4 minutes to form a curable resin composition layer having a thickness of 20 ⁇ m on the copper substrate. ..
- the curable resin composition layer on the m-copper substrate is formed by i-line (wavelength of about 365 nm).
- i-line wavelength of about 365 nm.
- exposure energy 400 mJ / cm 2
- the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere. After reaching 230 ° C., the temperature was maintained at 230 ° C. for 3 hours to obtain a copper substrate on which a cured film was formed.
- the curable resin composition layer on the m-copper substrate is formed by h-line (wavelength of about 405 nm).
- h-line wavelength of about 405 nm.
- exposure energy 400 mJ / cm 2
- the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere. After reaching 230 ° C., the temperature was maintained at 230 ° C. for 3 hours to obtain a copper substrate on which a cured film was formed.
- the curable resin composition layer on the m copper substrate is subjected to broadband light (high pressure mercury lamp). , 400 mJ / cm 2 exposure energy using a photomask having a 100 ⁇ m square non-masked portion, and further, under a nitrogen atmosphere, the temperature was raised at a heating rate of 10 ° C./min to 230. After reaching the temperature, the temperature was maintained at 230 ° C. for 3 hours to obtain a copper substrate on which a cured film was formed.
- broadband light high pressure mercury lamp
- the copper substrate on which the cured film was formed was heated in a constant temperature bath (ESPEC STH-120) for 500 hours in air at 150 ° C. and 90% relative humidity. Subsequently, the laminated body portion of the copper layer (copper substrate) and the cured film on the substrate was cut, and the cross section was further surface-treated with an ion milling apparatus (ArBlade5000, manufactured by Hitachi High-Technologies Corporation). The cross section of the laminated body of the obtained copper layer (Cu layer) and the cured film was observed from the side by FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Corporation), and the area ratio of voids to the surface of the Cu layer was observed. Was calculated.
- the area ratio of the voids was calculated by dividing the area of the void portion by the area of the entire Cu layer. From the above area ratio, evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the column of "corrosion suppression" in Tables 2 to 8. It can be said that the smaller the area ratio of the voids, the more the metal corrosion is suppressed.
- a curable resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a curable resin composition layer.
- the silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a curable resin composition layer having a uniform thickness of about 15 ⁇ m on the silicon wafer.
- the film thickness of the curable resin composition layer on the silicon wafer was measured, and this value was taken as the pre-aging film thickness.
- the film thickness was determined as an arithmetic mean value obtained by measuring the film thickness at 10 points on the coated surface with an ellipsometer (KT-22 manufactured by Foothill).
- the curable resin composition or the comparative composition was placed in a glass container, sealed, and allowed to stand in a light-shielded environment at 25 ° C. for 14 days, and then the pre-aging film thickness was determined.
- a curable resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method at the same number of revolutions as in the case of the above to form a curable resin composition layer.
- the silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a curable resin composition layer having a uniform thickness on the silicon wafer.
- the film thickness of the obtained curable resin composition layer was measured by the same method as the film thickness measuring method in the above-mentioned pre-aging film thickness measuring method, and this value was taken as the post-aging film thickness.
- Film thickness change rate (%)
- the calculated film thickness change rate was evaluated according to the following evaluation criteria, and the evaluation results are shown in the "Storage stability evaluation" column of Tables 2 to 8. It can be said that the smaller the rate of change in film thickness, the better the storage stability of the curable resin composition.
- a composition containing at least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof, a compound having a triazole structure, and a solvent according to the present invention According to the curable resin composition having a pH of less than 7.0, it can be seen that a cured film having excellent suppression of corrosion of adjacent metals can be obtained.
- the comparative compositions according to Comparative Examples 1 and 2 contain a compound having a triazole structure, and have a pH of 7.0 or higher. It can be seen that the comparative compositions according to Comparative Examples 1 and 2 are inferior in suppressing corrosion of the metal adjacent to the cured film and in liquid storage stability.
- the comparative compositions according to Comparative Examples 3 to 4 do not contain a compound having a triazole structure and have a pH of 7.0 or higher. It can be seen that the comparative compositions according to Comparative Examples 1 and 2 are inferior in suppressing corrosion of the metal adjacent to the cured film and in liquid storage stability.
- the comparative composition according to Comparative Example 5 has a pH of less than 7.0, but does not contain a compound having a triazole structure. It can be seen that the comparative composition according to Comparative Example 5 is inferior in suppressing corrosion of the metal adjacent to the cured film.
- Example 101 The curable resin composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin base material having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 5 minutes. After forming a curable resin composition layer having a thickness of 20 ⁇ m, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). The exposure was performed by irradiating light having a wavelength of 365 nm through a mask (a binary mask having a pattern of 1: 1 line and space and a line width of 10 ⁇ m). After exposure, it was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a layer pattern.
- NSR1505 i6, manufactured by Nikon Corporation a stepper
- the exposure was performed by irradiating light having a wavelength of 365 nm through a mask (a binary mask having a pattern of 1: 1 line and space and a line width of 10 ⁇ m). After exposure
- 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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Abstract
Description
これらの用途において、配線等として用いられる銅等の金属の腐食の抑制に優れた硬化膜が得られる硬化性樹脂組成物の提供が望まれている。 The cured film containing polyimide or polybenzoxazole is used, for example, in the above-mentioned insulating film, encapsulant material, protective film, flexible substrate base film, coverlay, and the like.
In these applications, it is desired to provide a curable resin composition capable of obtaining a cured film excellent in suppressing corrosion of metals such as copper used for wiring and the like.
<1> ポリイミド、ポリベンゾオキサゾール、及びこれらの前駆体よりなる群から選ばれた少なくとも1種の樹脂、
トリアゾール構造を有する化合物、並びに、
溶剤を含み、
組成物のpHが7.0未満である
硬化性樹脂組成物。
<2> 上記トリアゾール構造を有する化合物のジメチルスルホキシド中のpKaが15未満である、<1>に記載の硬化性樹脂組成物。
<3> 上記トリアゾール構造を有する化合物が1,2,3-トリアゾール構造を有する化合物を含む、<1>又は<2>に記載の硬化性樹脂組成物。
<4> 上記トリアゾール構造を有する化合物がベンゾトリアゾール構造を有する化合物を含む、<1>~<3>のいずれか1つに記載の硬化性樹脂組成物。
<5> 上記樹脂100質量部に対し、感光剤1~40質量部と、上記トリアゾール構造を有する化合物0.05~20質量部と、上記溶剤50~300質量部とを含む、<1>~<4>のいずれか1つに記載の硬化性樹脂組成物。
<6> 上記溶剤として、窒素原子を含まない溶剤を含む、<1>~<5>のいずれか1つに記載の硬化性樹脂組成物。
<7> 上記溶剤として、炭素原子、酸素原子及び水素原子のみから構成される溶剤を含む、<1>~<6>のいずれか1つに記載の硬化性樹脂組成物。
<8> 再配線層用層間絶縁膜の形成に用いられる、<1>~<7>のいずれか1つに記載の硬化性樹脂組成物。
<9> <1>~<8>のいずれか1つに記載の硬化性樹脂組成物を硬化してなる硬化膜。
<10> <9>に記載の硬化膜を2層以上含み、上記硬化膜同士のいずれかの間に金属層を含む積層体。
<11> <1>~<8>のいずれか1つに記載の硬化性樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。
<12> 上記膜を露光する露光工程及び上記膜を現像する現像工程を含む、<11>に記載の硬化膜の製造方法。
<13> 上記膜を50~450℃で加熱する加熱工程を含む、<11>又は<12>に記載の硬化膜の製造方法。
<14> <9>に記載の硬化膜又は<10>に記載の積層体を含む、半導体デバイス。 Examples of typical embodiments of the present invention are shown below.
<1> At least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.
Compounds having a triazole structure, as well as
Contains solvent,
A curable resin composition in which the pH of the composition is less than 7.0.
<2> The curable resin composition according to <1>, wherein the pKa in dimethyl sulfoxide of the compound having a triazole structure is less than 15.
<3> The curable resin composition according to <1> or <2>, wherein the compound having a triazole structure contains a compound having a 1,2,3-triazole structure.
<4> The curable resin composition according to any one of <1> to <3>, wherein the compound having a triazole structure contains a compound having a benzotriazole structure.
<5> A photosensitizer containing 1 to 40 parts by mass, a compound having a triazole structure of 0.05 to 20 parts by mass, and a solvent of 50 to 300 parts by mass with respect to 100 parts by mass of the resin. The curable resin composition according to any one of <4>.
<6> The curable resin composition according to any one of <1> to <5>, which contains a solvent containing no nitrogen atom as the solvent.
<7> The curable resin composition according to any one of <1> to <6>, which comprises a solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms as the solvent.
<8> The curable resin composition according to any one of <1> to <7>, which is used for forming an interlayer insulating film for a rewiring layer.
<9> A cured film obtained by curing the curable resin composition according to any one of <1> to <8>.
<10> A laminate containing two or more layers of the cured film according to <9> and containing a metal layer between any of the cured films.
<11> A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of <1> to <8> to a substrate to form a film.
<12> The method for producing a cured film according to <11>, which comprises an exposure step of exposing the film and a developing step of developing the film.
<13> The method for producing a cured film according to <11> or <12>, which comprises a heating step of heating the film at 50 to 450 ° C.
<14> A semiconductor device comprising the cured film according to <9> or the laminate according to <10>.
本明細書において「~」という記号を用いて表される数値範囲は、「~」の前後に記載される数値をそれぞれ下限値及び上限値として含む範囲を意味する。
本明細書において「工程」との語は、独立した工程だけではなく、その工程の所期の作用が達成できる限りにおいて、他の工程と明確に区別できない工程も含む意味である。
本明細書における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を有しない基(原子団)と共に置換基を有する基(原子団)をも包含する。例えば、「アルキル基」とは、置換基を有しないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含する。
本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた露光も含む。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線又は放射線が挙げられる。
本明細書において、「(メタ)アクリレート」は、「アクリレート」及び「メタクリレート」の両方、又は、いずれかを意味し、「(メタ)アクリル」は、「アクリル」及び「メタクリル」の両方、又は、いずれかを意味し、「(メタ)アクリロイル」は、「アクリロイル」及び「メタクリロイル」の両方、又は、いずれかを意味する。
本明細書において、構造式中のMeはメチル基を表し、Etはエチル基を表し、Buはブチル基を表し、Phはフェニル基を表す。
本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。また本明細書において、固形分濃度とは、組成物の総質量に対する、溶剤を除く他の成分の質量百分率である。
本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、特に述べない限り、ゲル浸透クロマトグラフィ(GPC測定)に従い、ポリスチレン換算値として定義される。本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、例えば、HLC-8220GPC(東ソー(株)製)を用い、カラムとしてガードカラムHZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000、TSKgel Super HZ2000(東ソー(株)製)を用いることによって求めることができる。それらの分子量は特に述べない限り、溶離液としてTHF(テトラヒドロフラン)を用いて測定したものとする。また、GPC測定における検出は特に述べない限り、UV線(紫外線)の波長254nm検出器を使用したものとする。
本明細書において、積層体を構成する各層の位置関係について、「上」又は「下」と記載したときには、注目している複数の層のうち基準となる層の上側又は下側に他の層があればよい。すなわち、基準となる層と上記他の層の間に、更に第3の層や要素が介在していてもよく、基準となる層と上記他の層は接している必要はない。また、特に断らない限り、基材に対し層が積み重なっていく方向を「上」と称し、又は、感光層がある場合には、基材から感光層へ向かう方向を「上」と称し、その反対方向を「下」と称する。なお、このような上下方向の設定は、本明細書中における便宜のためであり、実際の態様においては、本明細書における「上」方向は、鉛直上向きと異なることもありうる。
本明細書において、特段の記載がない限り、組成物は、組成物に含まれる各成分として、その成分に該当する2種以上の化合物を含んでもよい。また、特段の記載がない限り、組成物における各成分の含有量とは、その成分に該当する全ての化合物の合計含有量を意味する。
本明細書において、特に述べない限り、温度は23℃、気圧は101,325Pa(1気圧)、相対湿度は50%RHである。
本明細書において、好ましい態様の組み合わせは、より好ましい態様である。 Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
In the present specification, 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.
In the present specification, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, 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).
Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also exposure using particle beams such as an electron beam and an ion beam. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacryl", or , Either, and "(meth) acryloyl" means both "acryloyl" and "methacryloyl", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. Further, unless otherwise specified, the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as "upper". The opposite direction is referred to as "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "upward" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature is 23 ° C., the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
In the present specification, the combination of preferred embodiments is a more preferred embodiment.
本発明の硬化性樹脂組成物(以下、単に「本発明の組成物」ともいう。)は、ポリイミド、ポリベンゾオキサゾール、及びこれらの前駆体よりなる群から選ばれた少なくとも1種の樹脂、トリアゾール構造を有する化合物、並びに、溶剤を含み、組成物のpHが7.0未満である。
以下、ポリイミド、ポリベンゾオキサゾール、及びこれらの前駆体よりなる群から選ばれた少なくとも1種の樹脂を「特定樹脂」ともいう。 (Curable resin composition)
The curable resin composition of the present invention (hereinafter, also simply referred to as “the composition of the present invention”) is triazole, at least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof. It contains a compound having a structure and a solvent, and the pH of the composition is less than 7.0.
Hereinafter, at least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof is also referred to as "specific resin".
上記効果が得られるメカニズムは不明であるが、下記のように推測される。 According to the curable resin composition of the present invention, a cured film excellent in suppressing corrosion of adjacent metals can be obtained.
The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
このような用途において、デバイス中で配線等として用いられる銅等の金属と、硬化膜とが接する部分における上記金属の腐食が問題となる場合があった。
本発明者らは、このような金属の腐食と、硬化膜の形成に用いられる組成物の酸性度とが関連していることを見出した。
本発明者らは、組成物の酸性度が高い場合、銅等の金属がイオンとして組成物中にマイグレーションし、硬化膜中の成分、又は、硬化膜の外部から供給される水、酸素、若しくはハロゲンなどと反応し、脆弱な銅化合物を形成して、腐食が進行すると推測している。 The cured film containing polyimide or polybenzoxazole is used in various devices, for example, as an insulating film, a material for a sealing material, a protective film, a base film for a flexible substrate, a coverlay, and the like.
In such an application, corrosion of the metal at a portion where a metal such as copper used as wiring or the like in a device and a cured film is in contact may become a problem.
The present inventors have found that such metal corrosion is related to the acidity of the composition used for forming the cured film.
When the acidity of the composition is high, the present inventors migrate metal such as copper into the composition as ions, and the components in the cured film or water, oxygen, or water supplied from the outside of the cured film, or It is speculated that it reacts with halogens to form fragile copper compounds and corrosion progresses.
本発明者らは、トリアゾール構造を有する化合物は解離(例えば、脱プロトン化)すると銅等の金属との密着エネルギーが向上(J. Phys. Chem. C 2015, 119, 11625-11635)するため、上記特定のpHに調整した組成物においてトリアゾール構造を有する化合物を用いることにより、優れた腐食抑制能を有する硬化膜が得られると推測している。 Therefore, as a result of diligent studies by the present inventors, corrosion of metals such as copper is remarkably suppressed by using a composition containing a compound having a triazole structure and having a pH adjusted to less than 7. The present invention has been completed.
In the present invention, when a compound having a triazole structure is dissociated (for example, deprotonated), the adhesion energy with a metal such as copper is improved (J. Phys. Chem. C 2015, 119, 11625-11635). It is presumed that a cured film having an excellent ability to suppress corrosion can be obtained by using a compound having a triazole structure in the composition adjusted to the specific pH.
本発明の組成物によれば、特に高温高湿条件下(例えば、150℃、相対湿度90%RHなどの条件下)においても、トリアゾール構造を有する化合物と銅等の金属の腐食抑制能に優れる。
また、本発明の組成物によれば、例えば、硬化膜及び金属が高温条件下に晒された場合であっても、上記金属の腐食抑制効果により、金属と硬化膜との界面における空隙(ボイド)の発生が抑制されると考えられる。 Here, particularly when the device is used for a long period of time under high humidity or high temperature, corrosion of the metal due to melting of the metal such as copper becomes a problem.
According to the composition of the present invention, it is excellent in the ability to suppress corrosion of a compound having a triazole structure and a metal such as copper even under high temperature and high humidity conditions (for example, conditions such as 150 ° C. and 90% RH relative humidity). ..
Further, according to the composition of the present invention, for example, even when the cured film and the metal are exposed to high temperature conditions, voids (voids) at the interface between the metal and the cured film due to the corrosion suppressing effect of the metal. ) Is considered to be suppressed.
更に、ポリイミド又はポリベンゾオキサゾールを含む組成物においては、pHを7未満とすることにより、加水分解による主鎖切断(すなわち、分子量低下)が起きにくくなり、組成物の液保存安定性に優れると考えられる。 Further, in the composition containing the polyimide precursor or the polybenzoxazole precursor, the cyclization of the polyimide precursor and the polybenzoxazole precursor is suppressed by setting the pH to less than 7, and thus the liquid of the composition. It is considered to have excellent storage stability.
Further, in the composition containing polyimide or polybenzoxazole, when the pH is set to less than 7, main chain breakage (that is, decrease in molecular weight) due to hydrolysis is less likely to occur, and the composition is excellent in liquid storage stability. Conceivable.
以下、本発明の硬化性樹脂組成物について詳細に説明する。 Here, Patent Document 1 does not describe or suggest that the pH of the curable resin composition containing the specific resin is within the specific range.
Hereinafter, the curable resin composition of the present invention will be described in detail.
本発明の硬化性樹脂組成物のpHは、7.0未満であり、金属腐食抑制性、組成物の保存安定性の観点からは、6.8以下であることが好ましく、6.5以下であることがより好ましく、6.2以下であることが更に好ましく、6.0以下であることが特に好ましい。
上記pHの下限は特に限定されないが、2.0以上であることが好ましく、3.0以上であることがより好ましく、4.0以上であることが更に好ましく、4.5以上であることが特に好ましく、5.0以上であることが最も好ましい。
本発明において、組成物のpHは下記(1)~(4)に記載の方法により測定される。
(1)pH=4、7及び9の標準液を用いて校正した装置(HORIBA社製D-71)を使用する。
(2)上記装置の電極を、3.33mmol/Lの塩化カリウム(KCl)溶液に漬けておく。
(3)組成物を、組成物に含まれている溶剤で希釈して、pHの測定を行う。上記測定は、少なくとも希釈倍率を変更した3点において行う。
(4)上記装置を用いて、上記測定用溶液のpHを測定し、希釈倍率を考慮して希釈前のH+量から組成物のpHを算出する。
具体的には、上記(3)において測定された、希釈倍率を変更した3点以上の測定値に対してx= log10(希釈倍率)、 y=各希釈後の溶液のpHとした場合の直線回帰(y=ax+b)を行い、上記切片bを希釈前の組成物のpHとする。
上記直線回帰は最小二乗法により行う。 <pH>
The pH of the curable resin composition of the present invention is less than 7.0, preferably 6.8 or less, preferably 6.5 or less, from the viewpoint of metal corrosion inhibition and storage stability of the composition. It is more preferable, it is more preferably 6.2 or less, and it is particularly preferable that it is 6.0 or less.
The lower limit of the pH is not particularly limited, but is preferably 2.0 or higher, more preferably 3.0 or higher, further preferably 4.0 or higher, and preferably 4.5 or higher. It is particularly preferable, and most preferably 5.0 or more.
In the present invention, the pH of the composition is measured by the methods described in (1) to (4) below.
(1) An apparatus (D-71 manufactured by HORIBA) calibrated using standard solutions having pH = 4, 7 and 9 is used.
(2) The electrode of the above device is immersed in a 3.33 mmol / L potassium chloride (KCl) solution.
(3) The composition is diluted with the solvent contained in the composition, and the pH is measured. The above measurement is performed at least at three points where the dilution ratio is changed.
(4) Using the above apparatus, the pH of the measurement solution is measured, and the pH of the composition is calculated from the amount of H + before dilution in consideration of the dilution ratio.
Specifically, when x = log 10 (dilution ratio) and y = pH of the solution after each dilution with respect to the measured values of 3 points or more in which the dilution ratio was changed, which was measured in (3) above. A linear regression (y = ax + b) is performed and the section b is used as the pH of the composition before dilution.
The linear regression is performed by the method of least squares.
表1に、実施例1において使用した硬化性樹脂組成物において、希釈倍率(質量倍率)を3倍、30倍、300倍とした場合の希釈倍率のlog10(希釈倍率)、及び、各希釈後の溶液のpH(測定値)を記載する。 Hereinafter, the pH calculation method in Example 1 described later will be described.
In Table 1, in the curable resin composition used in Example 1, log 10 (dilution ratio) of the dilution ratio when the dilution ratio (mass ratio) is 3, 30, and 300 times, and each dilution. The pH (measured value) of the subsequent solution is described.
x=log10(希釈倍率)、y=各希釈後の溶液のpHとした場合の最小二乗法による直線回帰(y=ax+b)を行った結果、y=0.22x+6.0044となる。すなわち、実施例1に記載の組成物のpHは6.0である。
As a result of performing linear regression (y = ax + b) by the least squares method when x = log 10 (dilution ratio) and y = pH of the solution after each dilution, y = 0.22x + 6.0044 is obtained. That is, the pH of the composition described in Example 1 is 6.0.
本発明の硬化性樹脂組成物は、トリアゾール構造を有する化合物を含む。
以下、トリアゾール構造を有する化合物を「特定化合物」ともいう。
特定化合物におけるトリアゾール構造の数は、1以上であればよく、1~10であることが好ましく、1~4であることがより好ましく、1又は2であることが更に好ましく、1であることが特に好ましい。
本発明において、トリアゾール構造とは、窒素原子を3つ含む芳香族5員環構造であり、1,2,3-トリアゾール構造であってもよいし、1,2,4-トリアゾール構造であってもよいが、金属腐食抑制の観点からは、1,2,3-トリアゾール構造であることが好ましい。
1,2,3-トリアゾール構造には、1H-1,2,3トリアゾール構造と2H-1,2,3トリアゾール構造の2種類の互変異性体が存在するが、このいずれであってもよいし、これらの混合物であってもよい。
1H-1,2,3トリアゾール構造としては下記式(T-1)で表される構造が、2H-1,2,3トリアゾール構造としては下記式(T-2)で表される構造が、1,2,4トリアゾール構造としては下記式(T-3)で表される構造が、それぞれ挙げられる。
上記式(T-1)~(T-3)中、#及び*はそれぞれ、水素原子又は他の構造との結合部位を表す。
特定化合物におけるトリアゾール構造としては、式(T-1)、式(T-2)及び式(T-3)のいずれかで表される構造が好ましく、金属腐食抑制の観点からは、上記下記式(T-1)及び式(T-2)のいずれかで表される構造がより好ましい。 <Compound with triazole structure>
The curable resin composition of the present invention contains a compound having a triazole structure.
Hereinafter, a compound having a triazole structure is also referred to as a “specific compound”.
The number of triazole structures in the specific compound may be 1 or more, preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and preferably 1. Especially preferable.
In the present invention, the triazole structure is an aromatic 5-membered ring structure containing three nitrogen atoms, and may be a 1,2,3-triazole structure or a 1,2,4-triazole structure. However, from the viewpoint of suppressing metal corrosion, a 1,2,3-triazole structure is preferable.
There are two types of tautomers in the 1,2,3-triazole structure, 1H-1,2,3 triazole structure and 2H-1,2,3 triazole structure, and any of these may be used. However, it may be a mixture of these.
The 1H-1,2,3 triazole structure has a structure represented by the following formula (T-1), and the 2H-1,2,3 triazole structure has a structure represented by the following formula (T-2). Examples of the 1,2,4 triazole structure include structures represented by the following formula (T-3).
In the above formulas (T-1) to (T-3), # and * each represent a binding site with a hydrogen atom or another structure.
As the triazole structure in the specific compound, a structure represented by any of the formula (T-1), the formula (T-2) and the formula (T-3) is preferable, and from the viewpoint of suppressing metal corrosion, the above formula is described below. The structure represented by either (T-1) or (T-2) is more preferable.
金属腐食抑制の観点からは、特定化合物のジメチルスルホキシド(DMSO)中のpKaが、15未満であることが好ましく、8以上15未満であることがより好ましく、10以上15未満であることが更に好ましく、10以上14以下であることが特に好ましい。
ここで、pKaとは、酸の第一解離定数の逆数の対数を表し、Determination of Organic Structures by Physical Methods(著者:Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; 編纂:Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955)や、Data for Biochemical Research(著者:Dawson, R.M.C.et al; Oxford, Clarendon Press, 1959)に記載の値を参照することができる。これらの文献に記載の無い化合物については、ACD/pKa(ACD/Labs製)のソフトを用いて構造式より算出した値をpKaとして用いることとする。 [PKa]
From the viewpoint of suppressing metal corrosion, the pKa in dimethyl sulfoxide (DMSO) of the specific compound is preferably less than 15, more preferably 8 or more and less than 15, and further preferably 10 or more and less than 15. It is particularly preferably 10 or more and 14 or less.
Here, pKa represents the logarithm of the reciprocal of the first dissociation constant of acid, and the Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; compilation: Braude). , EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMCet al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using ACD / pKa (manufactured by ACD / Labs) software is used as pKa.
特定化合物は、下記式(T1-1)~式(T1-3)のいずれかで表される化合物又はこれらの塩を含むことが好ましく、式(T1-1)又は式(T1-2)で表される化合物又はこれらの塩を含むことがより好ましい。
式(T1-1)~式(T1-3)中、R11及びR12はそれぞれ独立に、水素原子又は1価の置換基を表し、R21及びR22はそれぞれ独立に、水素原子又は1価の置換基を表し、R31及びR32はそれぞれ独立に、1価の置換基を表し、RN1、RN2及びRN3はそれぞれ、水素原子又は1価の置換基を表し、R11、R12、RN1のうち少なくとも2つが結合して環構造を形成してもよく、R21、R22、RN2のうち少なくとも2つが結合して環構造を形成してもよく、R31、R32、RN3のうち少なくとも2つが結合して環構造を形成してもよい。 [Equation (T1-1) to Equation (T1-3)]
The specific compound preferably contains a compound represented by any of the following formulas (T1-1) to (T1-3) or a salt thereof, and is preferably represented by the formula (T1-1) or the formula (T1-2). It is more preferable to contain the compounds represented or salts thereof.
In formulas (T1-1) to (T1-3), R 11 and R 12 independently represent a hydrogen atom or a monovalent substituent, and R 21 and R 22 independently represent a hydrogen atom or 1 respectively. R 31 and R 32 each independently represent a valent substituent, and RN 1 , RN 2 and RN 3 each represent a hydrogen atom or a monovalent substituent, R 11 . R 12, may form at least two members ring structure of R N1, may be formed at least two bonded ring structure of R 21, R 22, R N2 , R 31, At least two of R 32 and RN 3 may be combined to form a ring structure.
上記炭化水素基としては、特に限定されないが、脂肪族炭化水素基又は芳香族炭化水素基が好ましく、炭素数1~20の脂肪族炭化水素基又は炭素数6~20の芳香族炭化水素基がより好ましい。
式(T1-1)中、RN1は水素原子又は1価の置換基を表し、水素原子が好ましい。
上記1価の置換基としては、上記R11における炭化水素基と同様の基が挙げられ、好ましい態様も同様である。
また、式(T1-1)中、R11、R12、RN1のうち少なくとも2つが結合して環構造を形成する場合、R11及びR12が結合して環構造を形成することが好ましい。
上記環構造としては、脂肪族炭化水素環構造、芳香族炭化水素環構造、脂肪族複素環構造、芳香族複素環構造のいずれであってもよいが、特定化合物のDMSO中のpKaを上述の範囲とする観点からは、芳香族炭化水素環構造が好ましい。
上記脂肪族炭化水素環構造としては、炭素数4~20の脂肪族炭化水素環構造が挙げられる。
上記芳香族炭化水素環構造としては、炭素数6~20の芳香族炭化水素環構造が挙げられ、ベンゼン環構造が好ましい。
上記脂肪族複素環構造としては、環員数5~20の脂肪族複素環構造が挙げられる。上記脂肪族複素環構造における複素原子としては、窒素原子、酸素原子、硫黄原子等が挙げられる。
上記芳香族複素環構造としては、環員数5~20の芳香族複素環構造が挙げられる。上記脂肪族複素環構造における複素原子としては、窒素原子、酸素原子、硫黄原子等が挙げられる。 In the formula (T1-1), R 11 and R 12 are preferably hydrogen atoms or hydrocarbon groups, respectively, and more preferably hydrocarbon groups.
The hydrocarbon group is not particularly limited, but an aliphatic hydrocarbon group or an aromatic hydrocarbon group is preferable, and an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable. More preferred.
Wherein (T1-1), R N1 represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom.
Examples of the monovalent substituent described above include the same groups as the hydrocarbon groups represented by R 11, preferable embodiments thereof are also the same.
Further, in the formula (T1-1), when at least two of R 11 , R 12 , and RN 1 are bonded to form a ring structure, it is preferable that R 11 and R 12 are bonded to form a ring structure. ..
The ring structure may be any of an aliphatic hydrocarbon ring structure, an aromatic hydrocarbon ring structure, an aliphatic heterocyclic structure, and an aromatic heterocyclic structure, and the pKa in the DMSO of the specific compound is described above. From the viewpoint of the range, the aromatic hydrocarbon ring structure is preferable.
Examples of the aliphatic hydrocarbon ring structure include an aliphatic hydrocarbon ring structure having 4 to 20 carbon atoms.
Examples of the aromatic hydrocarbon ring structure include an aromatic hydrocarbon ring structure having 6 to 20 carbon atoms, and a benzene ring structure is preferable.
Examples of the aliphatic heterocyclic structure include an aliphatic heterocyclic structure having 5 to 20 ring members. Examples of the complex atom in the above aliphatic heterocyclic structure include a nitrogen atom, an oxygen atom, a sulfur atom and the like.
Examples of the aromatic heterocyclic structure include an aromatic heterocyclic structure having 5 to 20 ring members. Examples of the complex atom in the above aliphatic heterocyclic structure include a nitrogen atom, an oxygen atom, a sulfur atom and the like.
式(T1-3)中、R31、R32及びRN3はそれぞれ、式(T1-1)中のR11、R12及びRN1と同義であり、好ましい態様も同様である。
また、式(T1-1)~式(T1-3)のいずれかで表される化合物の塩としては、ナトリウム塩、カリウム塩、マグネシウム塩等の公知の無機塩、又は、テトラブチルホスホニウム塩等の公知の有機塩が挙げられる。 Wherein (T1-2), each R 21, R 22 and R N2, have the same meaning as R 11, R 12 and R N1 in the formula (T1-1), preferable embodiments thereof are also the same.
Wherein (T1-3), each R 31, R 32 and R N3, have the same meaning as R 11, R 12 and R N1 in the formula (T1-1), preferable embodiments thereof are also the same.
Examples of the salt of the compound represented by any of the formulas (T1-1) to (T1-3) include known inorganic salts such as sodium salt, potassium salt and magnesium salt, or tetrabutylphosphonium salt and the like. Known organic salts of.
特定化合物のDMSO中のpKaを上述の範囲内とする観点からは、特定化合物は、ベンゾトリアゾール構造を有する化合物を含むことが好ましい。
ベンゾトリアゾール構造とは、上述のトリアゾール構造と、ベンゼン環構造とが縮合環を形成した構造をいう。
特定化合物がベンゾトリアゾール構造を有する場合、特定化合物におけるベンゾトリアゾール構造の数は、1以上であればよく、1~10であることが好ましく、1~4であることがより好ましく、1又は2であることが更に好ましく、1であることが特に好ましい。また、特定化合物がベンゾトリアゾール構造を有する場合、トリアゾール構造としてベンゾトリアゾール構造のみを有していてもよいし、ベンゾトリアゾール構造と、ベンゾトリアゾール構造以外のトリアゾール構造とを有していてもよい。
ベンゾトリアゾール構造には、1H-ベンゾトリアゾール構造と2H-ベンゾトリアゾール構造の2種類の互変異性体が存在するが、このいずれであってもよいし、これらの混合物であってもよい。
1H-ベンゾトリアゾール構造としては下記式(T-4)で表される構造が、2H-ベンゾトリアゾール構造としては下記式(T-5)で表される構造が、それぞれ挙げられる。
上記式(T-4)及び(T-5)中、#及び*はそれぞれ、水素原子又は他の構造との結合部位を表す。 [Benzotriazole structure]
From the viewpoint of keeping pKa in DMSO of the specific compound within the above range, the specific compound preferably contains a compound having a benzotriazole structure.
The benzotriazole structure refers to a structure in which the above-mentioned triazole structure and a benzene ring structure form a condensed ring.
When the specific compound has a benzotriazole structure, the number of benzotriazole structures in the specific compound may be 1 or more, preferably 1 to 10, more preferably 1 to 4, and 1 or 2. It is more preferably present, and particularly preferably 1. When the specific compound has a benzotriazole structure, it may have only a benzotriazole structure as a triazole structure, or may have a benzotriazole structure and a triazole structure other than the benzotriazole structure.
There are two types of tautomers of the 1H-benzotriazole structure and the 2H-benzotriazole structure in the benzotriazole structure, and any of these tautomers may be used, or a mixture thereof may be used.
Examples of the 1H-benzotriazole structure include a structure represented by the following formula (T-4), and examples of the 2H-benzotriazole structure include a structure represented by the following formula (T-5).
In the above formulas (T-4) and (T-5), # and * represent a binding site with a hydrogen atom or another structure, respectively.
特定化合物がベンゾトリアゾール構造を有する化合物である場合、特定化合物は、下記式(T1-4)及び式(T1-5)のいずれかで表される化合物又はこれらの塩を含むことが好ましい。
式(T1-4)及び式(T1-5)中、R41、R42、R43及びR44はそれぞれ独立に、水素原子又は1価の置換基を表し、R51、R52、R53及びR54はそれぞれ独立に、水素原子又は1価の置換基を表し、RN4及びRN5はそれぞれ、水素原子又は1価の置換基を表し、R41、R42、R43、R44及び、RN4のうち少なくとも2つが結合して環構造を形成してもよく、R51、R52、R53、R54及び、RN5のうち少なくとも2つが結合して環構造を形成してもよい。 [Equation (T1-4) and Equation (T1-5)]
When the specific compound is a compound having a benzotriazole structure, the specific compound preferably contains a compound represented by any of the following formulas (T1-4) and (T1-5) or a salt thereof.
In formulas (T1-4) and (T1-5), R 41 , R 42 , R 43 and R 44 each independently represent a hydrogen atom or a monovalent substituent, R 51 , R 52 , R 53. and R 54 each independently represent a hydrogen atom or a monovalent substituent, each R N4 and R N5 represent a hydrogen atom or a monovalent substituent, R 41, R 42, R 43, R 44 and , R N4 may be combined to form a ring structure, or at least two of R 51 , R 52 , R 53 , R 54 and RN 5 may be combined to form a ring structure. Good.
特定化合物の高温安定性の観点からは、R41、R42、R43及びR44のうち少なくとも1つが1価の置換基であることが好ましい。上記1価の置換基としては、炭化水素基が好ましく、アルキル基がより好ましく、炭素数1~10のアルキル基が更に好ましく、炭素数1~4のアルキル基が特に好ましく、メチル基が最も好ましい。
式(T1-4)中、RN4は水素原子又は1価の置換基を表し、水素原子が好ましい。
上記1価の置換基としては、上述の式(T1-1)中のR11における炭化水素基と同様の基が挙げられ、好ましい態様も同様である。
式(T1-4)中、R41、R42、R43、R44及び、RN4のうち少なくとも2つが結合して環構造を形成してもよいが、環構造を形成しないことが好ましい。
式(T1-4)中、R41、R42、R43、R44及び、RN4のうち少なくとも2つが結合して環構造を形成する場合、R41、R42、R43及びR44のうち少なくとも2つが結合して環構造を形成することが好ましい。
上記環構造としては、上述の式(T1-1)中のR11、R12、RN1のうち少なくとも2つが結合して形成される環構造と同様の環構造が挙げられ、好ましい態様も同様である。 In the formula (T1-4), R 41 , R 42 , R 43 and R 44 are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and the hydrogen atom or the number of carbon atoms. Alkyl groups of 1 to 10 are more preferable, alkyl groups having a hydrogen atom or 1 to 4 carbon atoms are particularly preferable, and hydrogen atoms or methyl groups are particularly preferable.
From the viewpoint of high temperature stability of the specific compound, it is preferable that at least one of R 41 , R 42 , R 43 and R 44 is a monovalent substituent. As the monovalent substituent, a hydrocarbon group is preferable, an alkyl group is more preferable, an alkyl group having 1 to 10 carbon atoms is further preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. ..
Wherein (T1-4), R N4 represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom.
Examples of the monovalent substituent include the same group as the hydrocarbon group in R 11 in the above formula (T1-1), and the preferred embodiment is also the same.
In formula (T1-4), at least two of R 41 , R 42 , R 43 , R 44, and RN 4 may be bonded to form a ring structure, but it is preferable not to form a ring structure.
In formula (T1-4), when at least two of R 41 , R 42 , R 43 , R 44 and RN 4 are combined to form a ring structure, of R 41 , R 42 , R 43 and R 44 . It is preferable that at least two of them are combined to form a ring structure.
As the ring structure, similar to the ring structure and the ring structure at least two are formed by bonding of R 11, R 12, R N1 in the above formula (T1-1) and the like, a preferred embodiment also the same Is.
トリアゾール構造を有する化合物としては、特に限定されないが、1H-ベンゾトリアゾール、2H-ベンゾトリアゾール、5ーメチル-1H-ベンゾトリアゾール、4-メチル-1H-ベンゾトリアゾール、7-メチル-1H-ベンゾトリアゾール、トリルトリアゾール、5,6-ジメチルベンゾオキサゾール、カルボキシベンゾトリアゾール、5-クロロ-2-メチルベンゾオキサゾール、1-メチル-1H-ベンゾトリアゾール、5-ニトロベンゾオキサゾール、1-アミノベンゾトリアゾール、4,5,6,7-テトラブロモベンゾトリアゾール、1H-1,2,3-トリアゾール、2H-1,2,3-トリアゾール、1,2,4-トリアゾール、トリス(1H-ベンゾトリアゾール-1-イル)メタン、これらの化合物の互変異性体等、これらの化合物の塩等が挙げられる。 〔Concrete example〕
The compound having a triazole structure is not particularly limited, but 1H-benzotriazole, 2H-benzotriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 7-methyl-1H-benzotriazole, tolyl. Triazole, 5,6-dimethylbenzotriazole, carboxybenzotriazole, 5-chloro-2-methylbenzotriazole, 1-methyl-1H-benzotriazole, 5-nitrobenzotriazole, 1-aminobenzotriazole, 4,5,6 , 7-Tetrabromobenzotriazole, 1H-1,2,3-triazole, 2H-1,2,3-triazole, 1,2,4-triazole, tris (1H-benzotriazole-1-yl) methane, these Examples thereof include benzotriazoles of the above compounds and salts of these compounds.
特定化合物の分子量は、69~1,000であることが好ましく、69~500であることがより好ましく、69~200であることが更に好ましい。 [Molecular weight]
The molecular weight of the specific compound is preferably 69 to 1,000, more preferably 69 to 500, and even more preferably 69 to 200.
特定化合物の含有量は、本発明の硬化性樹脂組成物の全固形分に対し、0.1~30質量%が好ましい。下限は、0.5質量%以上がより好ましく、1質量%以上が更に好ましい。上限は、20質量%以下がより好ましく、10質量%以下が更に好ましく、5質量%以下が特に好ましく、3質量%以下が最も好ましい。特定化合物は、1種又は2種以上を用いることができる。2種以上を用いる場合は、合計量が上記範囲であることが好ましい。 〔Content〕
The content of the specific compound is preferably 0.1 to 30% by mass with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 20% by mass or less, further preferably 10% by mass or less, particularly preferably 5% by mass or less, and most preferably 3% by mass or less. As the specific compound, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
本発明の硬化性樹脂組成物は、ポリイミド、ポリベンゾオキサゾール、及びこれらの前駆体よりなる群から選ばれた少なくとも1種の樹脂(特定樹脂)を含む。
本発明の硬化性樹脂組成物は、特定樹脂として、ポリイミド又はポリイミド前駆体を含むことが好ましく、ポリイミド前駆体を含むことがより好ましい。
また、特定樹脂はラジカル重合性基を有することが好ましい。
特定樹脂がラジカル重合性基を有する場合、硬化性樹脂組成物は、感光剤として後述の光ラジカル重合開始剤を含むことが好ましく、感光剤として後述の光ラジカル重合開始剤を含み、かつ、後述のラジカル架橋剤を含むことがより好ましく、感光剤として後述の光ラジカル重合開始剤を含み、後述のラジカル架橋剤を含み、かつ、後述の増感剤を含むことが更に好ましい。このような硬化性樹脂組成物からは、例えば、ネガ型感光層が形成される。
また、特定樹脂は、酸分解性基等の極性変換基を有していてもよい。
特定樹脂が酸分解性基を有する場合、硬化性樹脂組成物は、感光剤として後述の光酸発生剤を含むことが好ましい。このような硬化性樹脂組成物からは、例えば、化学増幅型であるポジ型感光層又はネガ型感光層が形成される。 <Resin>
The curable resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.
The curable resin composition of the present invention preferably contains a polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.
Further, the specific resin preferably has a radically polymerizable group.
When the specific resin has a radically polymerizable group, the curable resin composition preferably contains a photoradical polymerization initiator described later as a photosensitizer, contains a photoradical polymerization initiator described below as a photosensitizer, and is described later. It is more preferable to contain the radical cross-linking agent described above, and it is further preferable to contain the photoradical polymerization initiator described below as the photosensitizer, the radical cross-linking agent described below, and the sensitizer described below. From such a curable resin composition, for example, a negative type photosensitive layer is formed.
Further, the specific resin may have a polarity converting group such as an acid-degradable group.
When the specific resin has an acid-degradable group, the curable resin composition preferably contains a photoacid generator described later as a photosensitizer. From such a curable resin composition, for example, a chemically amplified positive type photosensitive layer or a negative type photosensitive layer is formed.
本発明で用いるポリイミド前駆体は、その種類等特に定めるものではないが、下記式(2)で表される繰り返し単位を含むことが好ましい。
式(2)
式(2)中、A1及びA2は、それぞれ独立に、酸素原子又はNHを表し、R111は、2価の有機基を表し、R115は、4価の有機基を表し、R113及びR114は、それぞれ独立に、水素原子又は1価の有機基を表す。 [Polyimide precursor]
The type of the polyimide precursor used in the present invention is not particularly specified, but it is preferable that the polyimide precursor contains a repeating unit represented by the following formula (2).
Equation (2)
In 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, and R 113. And R 114 independently represent a hydrogen atom or a monovalent organic group.
式(2)におけるR111は、2価の有機基を表す。2価の有機基としては、直鎖又は分岐の脂肪族基、環状の脂肪族基及び芳香族基を含む基が例示され、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数6~20の環状の脂肪族基、炭素数6~20の芳香族基、又は、これらの組み合わせからなる基が好ましく、炭素数6~20の芳香族基を含む基がより好ましい。本発明の特に好ましい実施形態として、-Ar-L-Ar-で表される基であることが例示される。但し、Arは、それぞれ独立に、芳香族基であり、Lは、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-CO-、-S-、-SO2-又はNHCO-、あるいは、上記の2つ以上の組み合わせからなる基である。これらの好ましい範囲は、上述のとおりである。 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. Examples of 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. A cyclic aliphatic group of 6 to 20, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. As a particularly preferable embodiment of the present invention, a group represented by -Ar-L-Ar- is exemplified. However, Ar is an aromatic group independently, and 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. These preferred ranges are as described above.
具体的には、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数6~20の環状の脂肪族基、炭素数6~20の芳香族基、又は、これらの組み合わせからなる基を含むジアミンであることが好ましく、炭素数6~20の芳香族基からなる基を含むジアミンであることがより好ましい。芳香族基の例としては、下記が挙げられる。 R 111 is preferably derived from diamine. Examples of 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 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. It is preferably a diamine containing, and more preferably a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of aromatic groups include:
式中、Aは、単結合、又は、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-C(=O)-、-S-、-SO2-、NHCO-、又は、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数1~3のアルキレン基、-O-、-C(=O)-、-S-、又は、-SO2-から選択される基であることがより好ましく、-CH2-、-O-、-S-、-SO2-、-C(CF3)2-、又は、-C(CH3)2-であることが更に好ましい。
式中、*は他の構造との結合部位を表す。
In the formula, A is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, —O—, —C (= O) −, —S—, —SO. 2 -, NHCO-, or is preferably a group selected from these combinations, a single bond, an alkylene group which ~ 1 carbon atoms which may be 3-substituted by fluorine atoms, -O -, - C ( = O) -, - S-, or, -SO 2 -, more preferably a group selected from, -CH 2 -, - O - , - S -, - SO 2 -, - C (CF 3 ) 2- or -C (CH 3 ) 2- is more preferable.
In the formula, * represents the binding site with other structures.
式(51)
式(51)中、R50~R57は、それぞれ独立に、水素原子、フッ素原子又は1価の有機基であり、R50~R57の少なくとも1つは、フッ素原子、メチル基又はトリフルオロメチル基である。
R50~R57の1価の有機基としては、炭素数1~10(好ましくは炭素数1~6)の無置換のアルキル基、炭素数1~10(好ましくは炭素数1~6)のフッ化アルキル基等が挙げられる。
式(61)中、R58及びR59は、それぞれ独立に、フッ素原子又はトリフルオロメチル基である。
式(51)又は(61)の構造を与えるジアミン化合物としては、2,2’-ジメチルベンジジン、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル、2,2’-ビス(フルオロ)-4,4’-ジアミノビフェニル、4,4’-ジアミノオクタフルオロビフェニル等が挙げられる。これらは1種で又は2種以上を組み合わせて用いてもよい。 Further, R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance. In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by the formula (61) is more preferable.
Equation (51)
In formula (51), R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, methyl group or trifluoro. It is a methyl group.
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.
In formula (61), R 58 and R 59 are independently fluorine atoms or trifluoromethyl groups, respectively.
Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.
式(5)又は式(6)中、*は他の構造との結合部位を表す。
式(5)
式(5)中、R112は、単結合、又は、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-CO-、-S-、-SO2-、及びNHCO-、ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数1~3のアルキレン基、-O-、-CO-、-S-及びSO2-から選択される基であることがより好ましく、-CH2-、-C(CF3)2-、-C(CH3)2-、-O-、-CO-、-S-及びSO2-からなる群から選択される2価の基であることが更に好ましい。 R 115 in the formula (2) represents a tetravalent organic group. As the 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.
In formula (5) or formula (6), * represents a binding site with another structure.
Equation (5)
In formula (5), R 112 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- , NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO More preferably, it is a group selected from-, -S- and SO 2- , -CH 2- , -C (CF 3 ) 2- , -C (CH 3 ) 2-, -O-, -CO. It is more preferably a divalent group selected from the group consisting of-, -S- and SO 2-.
テトラカルボン酸二無水物は、下記式(O)で表されることが好ましい。
式(O)
式(O)中、R115は、4価の有機基を表す。R115の好ましい範囲は式(2)におけるR115と同義であり、好ましい範囲も同様である。 Specific examples of R 115 include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
Equation (O)
In formula (O), R 115 represents a tetravalent organic group. A preferred range of R 115 has the same meaning as R 115 in formula (2), and preferred ranges are also the same.
エチレン性不飽和結合を有する基としては、ビニル基、(メタ)アリル基、下記式(III)で表される基などが挙げられ、下記式(III)で表される基が好ましい。 R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, and it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and both contain a polymerizable group. preferable. The polymerizable group is a group capable of a cross-linking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferable. Specific examples of the polymerizable group 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, a methylol group and an amino. The group is mentioned. As the radically polymerizable group contained in the polyimide precursor or the like, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
式(III)において、R201は、炭素数2~12のアルキレン基、-CH2CH(OH)CH2-又はポリアルキレンオキシ基を表す。
好適なR201の例は、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、1,2-ブタンジイル基、1,3-ブタンジイル基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、ドデカメチレン基、-CH2CH(OH)CH2-、ポリアルキレンオキシ基が挙げられ、エチレン基、プロピレン基、トリメチレン基、-CH2CH(OH)CH2-、ポリアルキレンオキシ基がより好ましく、有機膜において式(1)又は式(2)を満たしやすくする観点からは、ポリアルキレンオキシ基が更に好ましい。
本発明において、ポリアルキレンオキシ基とは、アルキレンオキシ基が2以上直接結合した基をいう。ポリアルキレンオキシ基に含まれる複数のアルキレンオキシ基におけるアルキレン基は、それぞれ同一であっても異なっていてもよい。
ポリアルキレンオキシ基が、アルキレン基が異なる複数種のアルキレンオキシ基を含む場合、ポリアルキレンオキシ基におけるアルキレンオキシ基の配列は、ランダムな配列であってもよいし、ブロックを有する配列であってもよいし、交互等のパターンを有する配列であってもよい。
上記アルキレン基の炭素数(アルキレン基が置換基を有する場合、置換基の炭素数を含む)は、2以上であることが好ましく、2~10であることがより好ましく、2~6であることがより好ましく、2~5であることが更に好ましく、2~4であることが一層好ましく、2又は3であることが特に好ましく、2であることが最も好ましい。
また、上記アルキレン基は、置換基を有していてもよい。好ましい置換基としては、アルキル基、アリール基、ハロゲン原子等が挙げられる。
また、ポリアルキレンオキシ基に含まれるアルキレンオキシ基の数(ポリアルキレンオキシ基の繰り返し数)は、2~20が好ましく、2~10がより好ましく、2~6が更に好ましい。
ポリアルキレンオキシ基としては、溶剤溶解性及び耐溶剤性の観点からは、ポリエチレンオキシ基、ポリプロピレンオキシ基、ポリトリメチレンオキシ基、ポリテトラメチレンオキシ基、又は、複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基が好ましく、ポリエチレンオキシ基又はポリプロピレンオキシ基がより好ましく、ポリエチレンオキシ基が更に好ましい。上記複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基において、エチレンオキシ基とプロピレンオキシ基とはランダムに配列していてもよいし、ブロックを形成して配列していてもよいし、交互等のパターン状に配列していてもよい。これらの基におけるエチレンオキシ基等の繰り返し数の好ましい態様は上述の通りである。 In formula (III), R200 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- or a polyalkyleneoxy group.
Examples of suitable R 201 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH 2 CH (OH) CH 2- , polyalkyleneoxy group, and ethylene group, propylene group, trimethylene group, -CH 2 CH (OH) CH 2- , polyalkyleneoxy group are more preferable, and organic film. From the viewpoint of facilitating the filling of the formula (1) or the formula (2), the polyalkyleneoxy group is more preferable.
In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, the arrangement 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. Is more preferable, 2 to 5 is more preferable, 2 to 4 is more preferable, 2 or 3 is particularly preferable, and 2 is most preferable.
Moreover, the said 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 (the number of repetitions of 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 polytrimethyleneoxy 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 in which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, 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.
R113又はR114が、水素原子、2-ヒドロキシベンジル、3-ヒドロキシベンジル及び4-ヒドロキシベンジルであることもより好ましい。 R 113 and R 114 are independently hydrogen atoms or monovalent organic groups. Examples of the monovalent organic group include an aromatic group and an aralkyl group in which an acidic group is bonded to one, two or three carbons constituting the aryl group, preferably one. Specific examples thereof include an aromatic group having an acidic group having 6 to 20 carbon atoms and an aralkyl group having an acidic group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group.
It is also more preferable that R 113 or R 114 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.
アルキル基の炭素数は1~30が好ましい。アルキル基は直鎖、分岐、環状のいずれであってもよい。直鎖又は分岐のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、オクタデシル基、イソプロピル基、イソブチル基、sec-ブチル基、t-ブチル基、1-エチルペンチル基、2-エチルヘキシル基2-(2-(2-メトキシエトキシ)エトキシ)エトキシ基、2-(2-(2-エトキシエトキシ)エトキシ)エトキシ)エトキシ基、2-(2-(2-(2-メトキシエトキシ)エトキシ)エトキシ)エトキシ基、及び2-(2-(2-(2-エトキシエトキシ)エトキシ)エトキシ)エトキシ基が挙げられる。環状のアルキル基は、単環の環状のアルキル基であってもよく、多環の環状のアルキル基であってもよい。単環の環状のアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基及びシクロオクチル基が挙げられる。多環の環状のアルキル基としては、例えば、アダマンチル基、ノルボルニル基、ボルニル基、カンフェニル基、デカヒドロナフチル基、トリシクロデカニル基、テトラシクロデカニル基、カンホロイル基、ジシクロヘキシル基及びピネニル基が挙げられる。中でも、高感度化との両立の観点から、シクロヘキシル基が最も好ましい。また、芳香族基で置換されたアルキル基としては、後述する芳香族基で置換された直鎖アルキル基が好ましい。
芳香族基としては、具体的には、置換又は無置換のベンゼン環、ナフタレン環、ペンタレン環、インデン環、アズレン環、ヘプタレン環、インダセン環、ペリレン環、ペンタセン環、アセナフテン環、フェナントレン環、アントラセン環、ナフタセン環、クリセン環、トリフェニレン環、フルオレン環、ビフェニル環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、インドリジン環、インドール環、ベンゾフラン環、ベンゾチオフェン環、イソベンゾフラン環、キノリジン環、キノリン環、フタラジン環、ナフチリジン環、キノキサリン環、キノキサゾリン環、イソキノリン環、カルバゾール環、フェナントリジン環、アクリジン環、フェナントロリン環、チアントレン環、クロメン環、キサンテン環、フェノキサチイン環、フェノチアジン環又はフェナジン環である。ベンゼン環が最も好ましい。 From the viewpoint of solubility in an organic solvent, R 113 or R 114 is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include 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, a dodecyl group, a tetradecyl group and an octadecyl group. , Isobutyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2- (2- (2-methoxyethoxy) ethoxy) ethoxy group, 2- (2- (2) -Ethoxyethoxy) ethoxy) ethoxy) ethoxy group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy group, and 2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) ethoxy ) Ethoxy group is mentioned. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving both high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
Specific examples of the aromatic group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene. Ring, naphthacene ring, chrysen ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin ring. , Indol ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, acrydin ring, phenanthrene ring, It is a thianthrene ring, a chromene ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring or a phenazine ring. The benzene ring is most preferable.
酸分解性基の具体例としては、tert-ブトキシカルボニル基、イソプロポキシカルボニル基、テトラヒドロピラニル基、テトラヒドロフラニル基、エトキシエチル基、メトキシエチル基、エトキシメチル基、トリメチルシリル基、tert-ブトキシカルボニルメチル基、トリメチルシリルエーテル基などが挙げられる。露光感度の観点からは、エトキシエチル基、又は、テトラヒドロフラニル基が好ましい。 At least one of R 113 and R 114 may be a polar converting group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it is decomposed by the action of an acid to produce 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 is more preferable from the viewpoint of exposure sensitivity.
Specific examples of the acid-degradable group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl. Examples include a group and a trimethylsilyl ether group. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.
式(2-A)
式(2-A)中、A1及びA2は、酸素原子を表し、R111及びR112は、それぞれ独立に、2価の有機基を表し、R113及びR114は、それぞれ独立に、水素原子又は1価の有機基を表し、R113及びR114の少なくとも一方は、重合性基を含む基であり、両方が重合性基であることが好ましい。 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). With such a structure, the width of the exposure latitude can be further widened.
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 polymerizable groups.
R112は、式(5)におけるR112と同義であり、好ましい範囲も同様である。 A 1, A 2, R 111 , R 113 and R 114 each independently have the same meaning as A 1, A 2, R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same ..
R 112 has the same meaning as R 112 in formula (5), and preferred ranges are also the same.
上記ポリイミド前駆体の分子量の分散度は、2.5以上が好ましく、2.7以上がより好ましく、2.8以上であることが更に好ましい。ポリイミド前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、4.5以下が好ましく、4.0以下がより好ましく、3.8以下が更に好ましく、3.2以下が一層好ましく、3.1以下がより一層好ましく、3.0以下が更に一層好ましく、2.95以下が特に好ましい。
本明細書において、分子量の分散度とは、重量平均分子量/数平均分子量により算出される値である。 The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000. 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 polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly defined, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is further preferable, and 3.2 or less is further preferable. Preferably, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.
In the present specification, the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
本発明に用いられるポリイミドは、アルカリ可溶性ポリイミドであってもよく、有機溶剤を主成分とする現像液に対して可溶なポリイミドであってもよい。
本明細書において、アルカリ可溶性ポリイミドとは、100gの2.38質量%テトラメチルアンモニウム水溶液に対し、23℃で0.1g以上溶解するポリイミドをいい、パターン形成性の観点からは、0.5g以上溶解するポリイミドであることが好ましく、1.0g以上溶解するポリイミドであることが更に好ましい。上記溶解量の上限は特に限定されないが、100g以下であることが好ましい。
また、ポリイミドは、得られる有機膜の膜強度及び絶縁性の観点からは、複数個のイミド構造を主鎖に有するポリイミドであることが好ましい。
本明細書において、「主鎖」とは、樹脂を構成する高分子化合物の分子中で相対的に最も長い結合鎖をいい、「側鎖」とはそれ以外の結合鎖をいう。 [Polyimide]
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.
In the present specification, the alkali-soluble polyimide means a polyimide that dissolves 0.1 g or more at 23 ° C. in 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and 0.5 g or more from the viewpoint of pattern forming property. A polyimide that dissolves is preferable, and a polyimide that dissolves 1.0 g or more is more preferable. The upper limit of the dissolution amount is not particularly limited, but is preferably 100 g or less.
Further, 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.
In the present specification, the "main chain" refers to the relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the "side chain" refers to other binding chains.
得られる有機膜の膜強度の観点からは、ポリイミドは、フッ素原子を有することが好ましい。
フッ素原子は、例えば、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131にフッ化アルキル基として含まれることがより好ましい。
ポリイミドの全質量に対するフッ素原子の量は、1~50mol/gであることが好ましく、5~30mol/gであることがより好ましい。 -Fluorine atom-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably 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 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 1 to 50 mol / g, and more preferably 5 to 30 mol / g.
得られる有機膜の膜強度の観点からは、ポリイミドは、ケイ素原子を有することが好ましい。
ケイ素原子は、例えば、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR131に後述する有機変性(ポリ)シロキサン構造として含まれることがより好ましい。
また、上記ケイ素原子又は上記有機変性(ポリ)シロキサン構造はポリイミドの側鎖に含まれていてもよいが、ポリイミドの主鎖に含まれることが好ましい。
ポリイミドの全質量に対するケイ素原子の量は、0.01~5mol/gであることが好ましく、0.05~1mol/gであることがより好ましい。 -Silicon atom-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably 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 0.01 to 5 mol / g, more preferably 0.05 to 1 mol / g.
得られる有機膜の膜強度の観点からは、ポリイミドは、エチレン性不飽和結合を有することが好ましい。
ポリイミドは、エチレン性不飽和結合を主鎖末端に有していてもよいし、側鎖に有していてもよいが、側鎖に有することが好ましい。
上記エチレン性不飽和結合は、ラジカル重合性を有することが好ましい。
エチレン性不飽和結合は、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131にエチレン性不飽和結合を有する基として含まれることがより好ましい。
これらの中でも、エチレン性不飽和結合は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR131にエチレン性不飽和結合を有する基として含まれることがより好ましい。
エチレン性不飽和結合を有する基としては、ビニル基、アリル基、ビニルフェニル基等の芳香環に直接結合した、置換されていてもよいビニル基を有する基、(メタ)アクリルアミド基、(メタ)アクリロイルオキシ基、下記式(IV)で表される基などが挙げられる。 -Ethylene unsaturated bond-
From the viewpoint of the film strength of the obtained organic film, 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 preferably provided at the side chain.
The ethylenically unsaturated bond preferably has radical polymerization property.
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. It is more preferable that 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.
Of these, ethylenically unsaturated bond, ethylene R 131 in the repeating unit represented by the preferably contained in R 131 in the repeating unit represented by the formula (4) described later, which will be described later Equation (4) 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 which is directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group and a (meth) group. Examples thereof include an acryloyloxy group and a group represented by the following formula (IV).
式(R1)~(R3)中、Lは単結合、又は、炭素数2~12のアルキレン基、炭素数2~30の(ポリ)アルキレンオキシ基若しくはこれらを2以上結合した基を表し、Xは酸素原子又は硫黄原子を表し、*は他の構造との結合部位を表し、●は式(III)中のR201が結合する酸素原子との結合部位を表す。
式(R1)~(R3)中、Lにおける炭素数2~12のアルキレン基、又は、炭素数2~30の(ポリ)アルキレンオキシ基の好ましい態様は、上述のR21における、炭素数2~12のアルキレン基、又は、炭素数2~30の(ポリ)アルキレンオキシ基の好ましい態様と同様である。
式(R1)中、Xは酸素原子であることが好ましい。
式(R1)~(R3)中、*は式(IV)中の*と同義であり、好ましい態様も同様である。
式(R1)で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、イソシアナト基及びエチレン性不飽和結合を有する化合物(例えば、2-イソシアナトエチルメタクリレート等)とを反応することにより得られる。
式(R2)で表される構造は、例えば、カルボキシ基を有するポリイミドと、ヒドロキシ基及びエチレン性不飽和結合を有する化合物(例えば、2-ヒドロキシエチルメタクリレート等)とを反応することにより得られる。
式(R3)で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、グリシジル基及びエチレン性不飽和結合を有する化合物(例えば、グリシジルメタクリレート等)とを反応することにより得られる。
ポリアルキレンオキシ基としては、溶剤溶解性及び耐溶剤性の観点からは、ポリエチレンオキシ基、ポリプロピレンオキシ基、ポリトリメチレンオキシ基、ポリテトラメチレンオキシ基、又は、複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基が好ましく、ポリエチレンオキシ基又はポリプロピレンオキシ基がより好ましく、ポリエチレンオキシ基が更に好ましい。上記複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基において、エチレンオキシ基とプロピレンオキシ基とはランダムに配列していてもよいし、ブロックを形成して配列していてもよいし、交互等のパターン状に配列していてもよい。これらの基におけるエチレンオキシ基等の繰り返し数の好ましい態様は上述の通りである。 Among these, 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).
In the formulas (R1) to (R3), 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, and X. Indicates an oxygen atom or a sulfur atom, * represents a bond site with another structure, and ● represents a bond site with an oxygen atom to which R 201 in the formula (III) is bonded.
In the formulas (R1) to (R3), 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 12 alkylene groups or (poly) alkyleneoxy groups having 2 to 30 carbon atoms.
In formula (R1), X is preferably an oxygen atom.
In formulas (R1) to (R3), * is synonymous with * in 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 obtained by reacting, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate). can get.
The polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy 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 in which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, 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.
また、製造適性の観点では、ポリイミドの全質量に対するエチレン性不飽和結合の量は、0.0001~0.1mol/gであることが好ましく、0.0005~0.05mol/gであることがより好ましい。 The amount of the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.
From the viewpoint of production suitability, the amount of ethylenically unsaturated bonds with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and preferably 0.0005 to 0.05 mol / g. More preferred.
ポリイミドは、エチレン性不飽和結合以外の架橋性基を有していてもよい。
エチレン性不飽和結合以外の架橋性基としては、エポキシ基、オキセタニル基等の環状エーテル基、メトキシメチル基等のアルコキシメチル基、メチロール基等が挙げられる。
エチレン性不飽和結合以外の架橋性基は、例えば、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましい。
ポリイミドの全質量に対するエチレン性不飽和結合以外の架橋性基の量は、0.05~10mol/gであることが好ましく、0.1~5mol/gであることがより好ましい。
また、製造適性の観点では、ポリイミドの全質量に対するエチレン性不飽和結合以外の架橋性基の量は、0.0001~0.1mol/gであることが好ましく、0.001~0.05mol/gであることがより好ましい。 -Crosslinkable groups other than ethylenically unsaturated bonds-
The polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.
Examples of the crosslinkable group other than the ethylenically unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
The crosslinkable group other than the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by the formula (4) described later, for example.
The amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.
From the viewpoint of production suitability, the amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. It is more preferably g.
ポリイミドは、酸分解性基等の極性変換基を有していてもよい。ポリイミドにおける酸分解性基は、上述の式(2)におけるR113及びR114において説明した酸分解性基と同様であり、好ましい態様も同様である。 -Polarity converter-
The polyimide may have a polarity converting group such as an acid-degradable group. The acid-degradable group in the polyimide is the same as the acid-degradable group described in R 113 and R 114 in the above formula (2), and the preferred embodiment is also the same.
ポリイミドがアルカリ現像に供される場合、現像性を向上する観点からは、ポリイミドの酸価は、30mgKOH/g以上であることが好ましく、50mgKOH/g以上であることがより好ましく、70mgKOH/g以上であることが更に好ましい。
また、上記酸価は500mgKOH/g以下であることが好ましく、400mgKOH/g以下であることがより好ましく、200mgKOH/g以下であることが更に好ましい。
また、ポリイミドが有機溶剤を主成分とする現像液を用いた現像(例えば、後述する「溶剤現像」)に供される場合、ポリイミドの酸価は、2~35mgKOH/gが好ましく、3~30mgKOH/gがより好ましく、5~20mgKOH/gが更に好ましい。
上記酸価は、公知の方法により測定され、例えば、JIS K 0070:1992に記載の方法により測定される。
また、ポリイミドに含まれる酸基としては、保存安定性及び現像性の両立の観点から、pKaが0~10である酸基が好ましく、3~8である酸基がより好ましい。
pKaとは、酸から水素イオンが放出される解離反応を考え、その平衡定数Kaをその負の常用対数pKaによって表したものである。
このような酸基として、ポリイミドは、カルボキシ基、及び、フェノール性ヒドロキシ基よりなる群から選ばれた少なくとも1種を含むことが好ましく、フェノール性ヒドロキシ基を含むことがより好ましい。 -Acid value-
When the polyimide is subjected to alkaline development, 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 the 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.
When the polyimide is subjected to development using a developing solution containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 2 to 35 mgKOH / g, and 3 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.
Further, as 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.
As such an acid group, 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.
アルカリ現像液による現像速度を適切なものとする観点からは、ポリイミドは、フェノール性ヒドロキシ基を有することが好ましい。
ポリイミドは、フェノール性ヒドロキシ基を主鎖末端に有してもよいし、側鎖に有してもよい。
フェノール性ヒドロキシ基は、例えば、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましい。
ポリイミドの全質量に対するフェノール性ヒドロキシ基の量は、0.1~30mol/gであることが好ましく、1~20mol/gであることがより好ましい。 -Phenolic hydroxy group-
From the viewpoint of making the development speed with an alkaline developer appropriate, 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.
式(4)
式(4)中、R131は、2価の有機基を表し、R132は、4価の有機基を表す。
重合性基を有する場合、重合性基は、R131及びR132の少なくとも一方に位置していてもよいし、下記式(4-1)又は式(4-2)に示すようにポリイミドの末端に位置していてもよい。
式(4-1)
式(4-1)中、R133は重合性基であり、他の基は式(4)と同義である。
式(4-2)
R134及びR135の少なくとも一方は重合性基であり、重合性基でない場合は有機基であり、他の基は式(4)と同義である。 The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably contains a repeating unit represented by the following formula (4), and is represented by the formula (4). More preferably, it is a compound containing a repeating unit and having a polymerizable group.
Equation (4)
In formula (4), R 131 represents a divalent organic group and R 132 represents a tetravalent organic group.
When having a polymerizable 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 (4-1)
In formula (4-1), R133 is a polymerizable group, and the other groups are synonymous with formula (4).
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).
R131は、2価の有機基を表す。2価の有機基としては、式(2)におけるR111と同様のものが例示され、好ましい範囲も同様である。
また、R131としては、ジアミンのアミノ基の除去後に残存するジアミン残基が挙げられる。ジアミンとしては、脂肪族、環式脂肪族又は芳香族ジアミンなどが挙げられる。
具体的な例としては、ポリイミド前駆体の式(2)中のR111の例が挙げられる。 The polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group possessed by the polyimide precursor and the like.
R 131 represents a divalent organic group. Examples of the divalent organic group include those similar to R 111 in the formula (2), and the preferred range is also the same.
Further, as R 131 , a diamine residue remaining after removal of the amino group of the diamine can be mentioned. Examples of the diamine include aliphatic, cyclic aliphatic or aromatic diamines.
Specific examples include an example of R 111 in the polyimide precursor formula (2).
例えば、R115として例示される4価の有機基の4つの結合子が、上記式(4)中の4つの-C(=O)-の部分と結合して縮合環を形成する。 R 132 represents a tetravalent organic group. Examples of the tetravalent organic group include those similar to R 115 in the formula (2), and the preferred range is also the same.
For example, four conjugates of a tetravalent organic group exemplified as R 115 combine with four −C (= O) − moieties in the above formula (4) to form a fused ring.
ポリイミドのイミド化率(「閉環率」ともいう)は、得られる有機膜の膜強度、絶縁性等の観点からは、70%以上であることが好ましく、80%以上であることがより好ましく、90%以上であることがより好ましい。
上記イミド化率の上限は特に限定されず、100%以下であればよい。
上記イミド化率は、例えば下記方法により測定される。
ポリイミドの赤外吸収スペクトルを測定し、イミド構造由来の吸収ピークである1377cm-1付近のピーク強度P1を求める。次に、そのポリイミドを350℃で1時間熱処理した後、再度、赤外吸収スペクトルを測定し、1377cm-1付近のピーク強度P2を求める。得られたピーク強度P1、P2を用い、下記式に基づいて、ポリイミドのイミド化率を求めることができる。
イミド化率(%)=(ピーク強度P1/ピーク強度P2)×100 -Immidization rate (ring closure rate)-
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 by, for example, 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. for 1 hour, and then the infrared absorption spectrum is measured again to obtain a peak intensity P2 in the vicinity of 1377 cm -1. Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be determined based on the following formula.
Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100
ポリイミドの市販品としては、Durimide(登録商標)284(富士フイルム(株)製)、Matrimide5218(HUNTSMAN(株)製)が例示される。 Polyimide is, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound (partially replaced with a terminal encapsulant which is monoamine) at a low temperature, or a tetracarboxylic acid dianhydride (partly an acid) at a low temperature. A method of reacting a diamine compound with an anhydride or a monoacid chloride compound or a terminal capping agent which is a monoactive ester compound), a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then diamine (partly monoamine) is obtained. A method of reacting in the presence of a condensing agent with (replaced with an end-capping agent), a diester is obtained by tetracarboxylic acid dianhydride and alcohol, and then the remaining dicarboxylic acid is acid-chlorided to diamine (partly monoamine). A polyimide precursor is obtained by using a method such as a method of reacting with an end-capping agent (replaced with an end-capping agent), and the polyimide precursor is completely imidized by using a known imidization reaction method, or an imide in the middle. Synthesis using a method of stopping the conversion reaction and introducing a partially imidized structure, and further, a method of introducing a partially imidized structure by blending a completely imidized polymer with its polyimide precursor. Can be done.
Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by HUNTSMAN Co., Ltd.).
本発明で用いるポリベンゾオキサゾール前駆体は、その構造等について特に定めるものではないが、好ましくは下記式(3)で表される繰り返し単位を含む。
式(3)
式(3)中、R121は、2価の有機基を表し、R122は、4価の有機基を表し、R123及びR124は、それぞれ独立に、水素原子又は1価の有機基を表す。 [Polybenzoxazole precursor]
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).
Equation (3)
In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group. Represent.
式(3)において、R121は、2価の有機基を表す。2価の有機基としては、脂肪族基及び芳香族基の少なくとも一方を含む基が好ましい。脂肪族基としては、直鎖の脂肪族基が好ましい。R121は、ジカルボン酸残基が好ましい。ジカルボン酸残基は、1種のみ用いてもよいし、2種以上用いてもよい。 In the formula (3), 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.
In formula (3), R 121 represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As 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.
脂肪族基を含むジカルボン酸としては、直鎖又は分岐(好ましくは直鎖)の脂肪族基を含むジカルボン酸が好ましく、直鎖又は分岐(好ましくは直鎖)の脂肪族基と2つの-COOHからなるジカルボン酸がより好ましい。直鎖又は分岐(好ましくは直鎖)の脂肪族基の炭素数は、2~30であることが好ましく、2~25であることがより好ましく、3~20であることが更に好ましく、4~15であることが一層好ましく、5~10であることが特に好ましい。直鎖の脂肪族基はアルキレン基であることが好ましい。
直鎖の脂肪族基を含むジカルボン酸としては、マロン酸、ジメチルマロン酸、エチルマロン酸、イソプロピルマロン酸、ジ-n-ブチルマロン酸、スクシン酸、テトラフルオロスクシン酸、メチルスクシン酸、2,2-ジメチルスクシン酸、2,3-ジメチルスクシン酸、ジメチルメチルスクシン酸、グルタル酸、ヘキサフルオログルタル酸、2-メチルグルタル酸、3-メチルグルタル酸、2,2-ジメチルグルタル酸、3,3-ジメチルグルタル酸、3-エチル-3-メチルグルタル酸、アジピン酸、オクタフルオロアジピン酸、3-メチルアジピン酸、ピメリン酸、2,2,6,6-テトラメチルピメリン酸、スベリン酸、ドデカフルオロスベリン酸、アゼライン酸、セバシン酸、ヘキサデカフルオロセバシン酸、1,9-ノナン二酸、ドデカン二酸、トリデカン二酸、テトラデカン二酸、ペンタデカン二酸、ヘキサデカン二酸、ヘプタデカン二酸、オクタデカン二酸、ノナデカン二酸、エイコサン二酸、ヘンエイコサン二酸、ドコサン二酸、トリコサン二酸、テトラコサン二酸、ペンタコサン二酸、ヘキサコサン二酸、ヘプタコサン二酸、オクタコサン二酸、ノナコサン二酸、トリアコンタン二酸、ヘントリアコンタン二酸、ドトリアコンタン二酸、ジグリコール酸、更に下記式で表されるジカルボン酸等が挙げられる。 As the 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.
As the 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 composed 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, further 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.
Examples of the dicarboxylic acid containing a linear aliphatic group 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-Dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadiponic acid, 3-methyladiponic acid, pimelli acid, 2,2,6,6-tetramethylpimeric acid, suberin Acid, dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonane diic acid, dodecane diic acid, tridecane diic acid, tetradecane diic acid, pentadecane diic acid, hexadecane diic acid, heptadecane diic acid , Octadecan diic acid, nonadecan diic acid, eikosan diic acid, henei cosan diic acid, docosan diic acid, tricosan diic acid, tetracosan diic acid, pentacosan diic acid, hexacosan diic acid, heptacosan diic acid, octacosan diic acid, nonacosan diic acid, tria Examples thereof include contan diic acid, hentoria contan diic acid, dotria contan diic acid, diglycolic acid, and dicarboxylic acid represented by the following formula.
(式中、Zは炭素数1~6の炭化水素基であり、nは1~6の整数である。)
(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).
式中、Aは-CH2-、-O-、-S-、-SO2-、-CO-、-NHCO-、-C(CF3)2-、及び、-C(CH3)2-からなる群から選択される2価の基を表し、*はそれぞれ独立に、他の構造との結合部位を表す。
In the formula, A is -CH 2- , -O-, -S-, -SO 2- , -CO-, -NHCO-, -C (CF 3 ) 2- , and -C (CH 3 ) 2- Represents a divalent group selected from the group consisting of, and each independently represents a binding site with another structure.
R122は、また、ビスアミノフェノール誘導体由来の基であることが好ましく、ビスアミノフェノール誘導体由来の基としては、例えば、3,3’-ジアミノ-4,4’-ジヒドロキシビフェニル、4,4’-ジアミノ-3,3’-ジヒドロキシビフェニル、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルスルホン、4,4’-ジアミノ-3,3’-ジヒドロキシジフェニルスルホン、ビス-(3-アミノ-4-ヒドロキシフェニル)メタン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)プロパン、2,2-ビス-(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン、2,2-ビス-(4-アミノ-3-ヒドロキシフェニル)ヘキサフルオロプロパン、ビス-(4-アミノ-3-ヒドロキシフェニル)メタン、2,2-ビス-(4-アミノ-3-ヒドロキシフェニル)プロパン、4,4’-ジアミノ-3,3’-ジヒドロキシベンゾフェノン、3,3’-ジアミノ-4,4’-ジヒドロキシベンゾフェノン、4,4’-ジアミノ-3,3’-ジヒドロキシジフェニルエーテル、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルエーテル、1,4-ジアミノ-2,5-ジヒドロキシベンゼン、1,3-ジアミノ-2,4-ジヒドロキシベンゼン、1,3-ジアミノ-4,6-ジヒドロキシベンゼンなどが挙げられる。これらのビスアミノフェノールは、単独にて、あるいは混合して使用してもよい。 In formula (3), 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 the bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino-) 4-Hydroxyphenyl) methane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-Amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-Diamino-3,3'-dihydroxybenzophenone,3,3'-diamino-4,4'-dihydroxybenzophenone,4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-dihydroxy-4, Examples thereof include 4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.
式中、X1は、-O-、-S-、-C(CF3)2-、-CH2-、-SO2-、-NHCO-を表し、*及び#はそれぞれ、他の構造との結合部位を表す。Rは水素原子又は1価の置換基を表し、水素原子又は炭化水素基が好ましく、水素原子又はアルキル基がより好ましい。また、R122は、上記式により表される構造であることも好ましい。R122が、上記式により表される構造である場合、計4つの*及び#のうち、いずれか2つが式(3)中のR122が結合する窒素原子との結合部位であり、かつ、別の2つが式(3)中のR122が結合する酸素原子との結合部位であることが好ましく、2つの*が式(3)中のR122が結合する酸素原子との結合部位であり、かつ、2つの#が式(3)中のR122が結合する窒素原子との結合部位であるか、又は、2つの*が式(3)中のR122が結合する窒素原子との結合部位であり、かつ、2つの#が式(3)中のR122が結合する酸素原子との結合部位であることがより好ましく、2つの*が式(3)中のR122が結合する酸素原子との結合部位であり、かつ、2つの#が式(3)中のR122が結合する窒素原子との結合部位であることが更に好ましい。
In the formula, X 1 represents -O-, -S-, -C (CF 3 ) 2- , -CH 2- , -SO 2- , -NHCO-, and * and # represent other structures, respectively. Represents the binding site of. 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. When R 122 has a structure represented by the above formula, any two of the four * and # in total are the binding sites with the nitrogen atom to which R 122 in the formula (3) is bonded, and preferably R 122 in another 2 Exemplary ethynylphenylbiadamantane derivatives (3) is a binding site to the oxygen atom bonding, two * is a bond sites with an oxygen atom R 122 are attached in the formula (3) , And two # are the binding sites with the nitrogen atom to which R 122 in the formula (3) is bound, or two * are the binding sites with the nitrogen atom to which R 122 in the formula (3) is bound. It is more preferable that the site is a site and the two #s are the binding sites with the oxygen atom to which 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 the binding site is a binding site with an atom and the two #s are the binding sites with a nitrogen atom to which R 122 in the formula (3) is bonded.
(式(A-sc)中、*は上記式(A-s)で示されるビスアミノフェノール誘導体のアミノフェノール基の芳香環に結合することを示す。)
(In the formula (A-sc), * indicates that it binds to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)
閉環に伴う反りの発生を抑制できる点で、下記式(SL)で表されるジアミン残基を他の種類の繰り返し構造単位として含むことが好ましい。 The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3).
It is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit in that the occurrence of warpage due to ring closure can be suppressed.
式(SL)中、Zは、a構造とb構造を有し、R1sは、水素原子又は炭素数1~10の炭化水素基であり、R2sは炭素数1~10の炭化水素基であり、R3s、R4s、R5s、R6sのうち少なくとも1つは芳香族基で、残りは水素原子又は炭素数1~30の有機基で、それぞれ同一でも異なっていてもよい。a構造及びb構造の重合は、ブロック重合でもランダム重合でもよい。Z部分のモル%は、a構造は5~95モル%、b構造は95~5モル%であり、a+bは100モル%である。
In formula (SL), 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, and R 2s is a hydrocarbon group having 1 to 10 carbon atoms. Yes , at least one of R 3s, R 4s , R 5s , and R 6s is an aromatic group, and 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.
上記ポリベンゾオキサゾール前駆体の分子量の分散度は、1.4以上であることが好ましく、1.5以上がより好ましく、1.6以上であることが更に好ましい。ポリベンゾオキサゾール前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、2.6以下が好ましく、2.5以下がより好ましく、2.4以下が更に好ましく、2.3以下が一層好ましく、2.2以下がより一層好ましい。 The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further, when used in the compositions described below. It is preferably 22,000 to 28,000. 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, and further 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, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. Is more preferable, and 2.2 or less is even more preferable.
ポリベンゾオキサゾールとしては、ベンゾオキサゾール環を有する高分子化合物であれば、特に限定はないが、下記式(X)で表される化合物であることが好ましく、下記式(X)で表される化合物であって、重合性基を有する化合物であることがより好ましい。上記重合性基としては、ラジカル重合性基が好ましい。また、下記式(X)で表される化合物であって、酸分解性基等の極性変換基を有する化合物であってもよい。
式(X)中、R133は、2価の有機基を表し、R134は、4価の有機基を表す。
重合性基又は酸分解性基等の極性変換基を有する場合、重合性基又は酸分解性基等の極性変換基は、R133及びR134の少なくとも一方に位置していてもよいし、下記式(X-1)又は式(X-2)に示すようにポリベンゾオキサゾールの末端に位置していてもよい。
式(X-1)
式(X-1)中、R135及びR136の少なくとも一方は、重合性基又は酸分解性基等の極性変換基であり、重合性基又は酸分解性基等の極性変換基でない場合は有機基であり、他の基は式(X)と同義である。
式(X-2)
式(X-2)中、R137は重合性基又は酸分解性基等の極性変換基であり、他は置換基であり、他の基は式(X)と同義である。 [Polybenzoxazole]
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. Further, it may be a compound represented by the following formula (X) and having a polarity converting group such as an acid-degradable group.
In formula (X), R 133 represents a divalent organic group and R 134 represents a tetravalent organic group.
When having a polar converting group such as a polymerizable group or an acid-degradable group, the polar converting group such as a polymerizable group or an acid-degradable group may be located at at least one of R 133 and R 134 , and may be located at least one of the following. It may be located at the end of the polybenzoxazole as shown in the formula (X-1) or the formula (X-2).
Equation (X-1)
In formula (X-1), at least one of R 135 and R 136 is a polar converting group such as a polymerizable group or an acid-degradable group, and is not a polar converting group such as a polymerizable group or an acid-degradable group. It is an organic group, and the other groups are synonymous with the formula (X).
Equation (X-2)
In the formula (X-2), R 137 is a polar converting group such as a polymerizable group or an acid-degradable group, the other is a substituent, and the other group is synonymous with the formula (X).
例えば、R122として例示される4価の有機基の4つの結合子が、上記式(X)中の窒素原子、酸素原子と結合して縮合環を形成する。例えば、R134が、下記有機基である場合、下記構造を形成する。
For example, 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 condensed ring. For example, when R 134 is the following organic group, it forms the following structure.
なお、ジカルボン酸の場合には反応収率等を高めるため、1-ヒドロキシ-1,2,3-ベンゾトリアゾール等を予め反応させた活性エステル型のジカルボン酸誘導体を用いてもよい。 The resulting polybenzoxazole, for example, a bis-aminophenol derivative, a dicarboxylic acid or the dicarboxylic acid containing R 133, is reacted with a compound selected from such dicarboxylic acid dichloride and dicarboxylic acid derivatives, the polybenzoxazole precursor , This is obtained by oxazoleization using a known oxazoleization reaction method.
In the case of a dicarboxylic acid, an active ester-type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.
ポリイミド前駆体等は、ジカルボン酸又はジカルボン酸誘導体とジアミンとを反応させて得られる。好ましくは、ジカルボン酸又はジカルボン酸誘導体を、塩化チオニル等のハロゲン化剤を用いてハロゲン化させた後、ジアミンと反応させて得られる。 [Manufacturing method of polyimide precursor, etc.]
A polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent such as thionyl chloride and then reacting it with a diamine.
有機溶剤は1種でもよいし、2種以上でもよい。
有機溶剤としては、原料に応じて適宜定めることができるが、ピリジン、ジエチレングリコールジメチルエーテル(ジグリム)、N-メチルピロリドン及びN-エチルピロリドンが例示される。
ポリイミドは、ポリイミド前駆体を合成してから、熱イミド化、化学イミド化(例えば、触媒を作用させることによる環化反応の促進)等の方法により環化させて製造してもよいし、直接、ポリイミドを合成してもよい。 In the method for producing a polyimide precursor or the like, it is preferable to use 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, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
The polyimide may be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (for example, promotion of cyclization reaction by acting a catalyst), or directly. , Polyimide may be synthesized.
ポリイミド前駆体等の製造方法に際し、保存安定性をより向上させるため、酸無水物、モノカルボン酸、モノ酸クロリド化合物、モノ活性エステル化合物などの末端封止剤で、ポリイミド前駆体等の末端を封止することが好ましい。末端封止剤としては、モノアミンを用いることがより好ましく、モノアミンの好ましい化合物としては、アニリン、2-エチニルアニリン、3-エチニルアニリン、4-エチニルアニリン、5-アミノ-8-ヒドロキシキノリン、1-ヒドロキシ-7-アミノナフタレン、1-ヒドロキシ-6-アミノナフタレン、1-ヒドロキシ-5-アミノナフタレン、1-ヒドロキシ-4-アミノナフタレン、2-ヒドロキシ-7-アミノナフタレン、2-ヒドロキシ-6-アミノナフタレン、2-ヒドロキシ-5-アミノナフタレン、1-カルボキシ-7-アミノナフタレン、1-カルボキシ-6-アミノナフタレン、1-カルボキシ-5-アミノナフタレン、2-カルボキシ-7-アミノナフタレン、2-カルボキシ-6-アミノナフタレン、2-カルボキシ-5-アミノナフタレン、2-アミノ安息香酸、3-アミノ安息香酸、4-アミノ安息香酸、4-アミノサリチル酸、5-アミノサリチル酸、6-アミノサリチル酸、2-アミノベンゼンスルホン酸、3-アミノベンゼンスルホン酸、4-アミノベンゼンスルホン酸、3-アミノ-4,6-ジヒドロキシピリミジン、2-アミノフェノール、3-アミノフェノール、4-アミノフェノール、2-アミノチオフェノール、3-アミノチオフェノール、4-アミノチオフェノールなどが挙げられる。これらを2種以上用いてもよく、複数の末端封止剤を反応させることにより、複数の異なる末端基を導入してもよい。 -End sealant-
In order to further improve the storage stability in the production method of the polyimide precursor, etc., the end of the polyimide precursor, etc. is used as an end sealant such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. It is preferable to seal. It is more preferable to use monoamine as the terminal encapsulant, and preferred compounds of monoamine are aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-. Hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amino Naphthalene, 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-Aminonaphthalene, 2-Aminobenzoic acid, 3-Aminobenzoic acid, 4-Aminobenzoic acid, 4-Aminosalicylic acid, 5-Aminosalicylic acid, 6-Aminosalicylic acid, 2- Aminobenzene sulfonic acid, 3-aminobenzene sulfonic acid, 4-aminobenzene sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol , 3-Aminothiophenol, 4-Aminothiophenol and the like. Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end sealants.
ポリイミド前駆体等の製造に際し、固体を析出する工程を含んでいてもよい。具体的には、反応液中のポリイミド前駆体等を、水中に沈殿させ、テトラヒドロフラン等のポリイミド前駆体等が可溶な溶剤に溶解させることによって、固体析出することができる。
その後、ポリイミド前駆体等を乾燥して、粉末状のポリイミド前駆体等を得ることができる。 -Solid precipitation-
A step of precipitating a solid may be included in the production of the polyimide precursor or the like. Specifically, the polyimide precursor or the like in the reaction solution is precipitated in water, and the polyimide precursor or the like such as tetrahydrofuran is dissolved in a soluble solvent to cause solid precipitation.
Then, the polyimide precursor or the like can be dried to obtain a powdery polyimide precursor or the like.
本発明の組成物における特定樹脂の含有量は、組成物の全固形分に対し20質量%以上であることが好ましく、30質量%以上であることがより好ましく、40質量%以上であることが更に好ましく、50質量%以上であることが一層好ましい。また、本発明の組成物における樹脂の含有量は、組成物の全固形分に対し、99.5質量%以下であることが好ましく、99質量%以下であることがより好ましく、98質量%以下であることが更に好ましく、97質量%以下であることが一層好ましく、95質量%以下であることがより一層好ましい。
本発明の組成物は、特定樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。 〔Content〕
The content of the specific resin in the 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 composition. More preferably, it is more preferably 50% by mass or more. The resin content in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass or less, based on the total solid content of the composition. It is more preferably 97% by mass or less, and even more preferably 95% by mass or less.
The composition of the present invention may contain only one type of the specific resin, or may contain two or more types of the specific resin. When two or more types are included, the total amount is preferably in the above range.
本発明の樹脂組成物は、上述した特定樹脂と、特定樹脂とは異なる他の樹脂(以下、単に「他の樹脂」ともいう)とを含んでもよい。
他の樹脂としては、フェノール樹脂、ポリアミド、エポキシ樹脂、ポリシロキサン、シロキサン構造を含む樹脂、アクリル樹脂等が挙げられる。
例えば、アクリル樹脂を更に加えることにより、塗布性に優れた組成物が得られ、また、耐溶剤性に優れたパターン(硬化膜)が得られる。
例えば、後述する重合性化合物に代えて、又は、後述する重合性化合物に加えて、重量平均分子量が20,000以下の重合性基価の高いアクリル系樹脂を組成物に添加することにより、組成物の塗布性、パターン(硬化膜)の耐溶剤性等を向上させることができる。 <Other resins>
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”).
Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, and acrylic resins.
For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, and a pattern (cured film) having excellent solvent resistance can be obtained.
For example, the composition is formed by adding an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable base value to the composition in place of the polymerizable compound described later or in addition to the polymerizable compound described later. It is possible to improve the coatability of an object, the solvent resistance of a pattern (cured film), and the like.
また、本発明の樹脂組成物における、他の樹脂の含有量は、組成物の全固形分に対し、80質量%以下であることが好ましく、75質量%以下であることがより好ましく、70質量%以下であることが更に好ましく、60質量%以下であることが一層好ましく、50質量%以下であることがより一層好ましい。
また、本発明の樹脂組成物の好ましい一態様として、他の樹脂の含有量が低含有量である態様とすることもできる。上記態様において、他の樹脂の含有量は、組成物の全固形分に対し、20質量%以下であることが好ましく、15質量%以下であることがより好ましく、10質量%以下であることが更に好ましく、5質量%以下であることが一層好ましく、1質量%以下であることがより一層好ましい。上記含有量の下限は特に限定されず、0質量%以上であればよい。
本発明の樹脂組成物は、他の樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。 When the resin composition of the present invention contains another resin, 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 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. preferable.
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 70% by mass, based on the total solid content of the composition. % Or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
Further, as a preferable aspect of the resin composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and preferably 10% by mass or less, based on the total solid content of the composition. More preferably, it is more preferably 5% by mass or less, and even more preferably 1% by mass or less. 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 types are included, the total amount is preferably in the above range.
本発明の硬化性樹脂組成物は、溶剤を含む。溶剤としては、公知の溶剤を任意に使用できる。溶剤は有機溶剤が好ましい。有機溶剤としては、エステル類、エーテル類、ケトン類、芳香族炭化水素類、スルホキシド類、アミド類、アルコール類などの化合物が挙げられる。 <Solvent>
The curable resin composition of the present invention contains a solvent. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, amides, and alcohols.
上記水の含有量は、3質量%以下であることが好ましく、1質量%以下であることがより好ましく、0.1質量%以下であることが更に好ましい。
また、上記水の含有量は、0質量%としてもよい。 The curable resin composition of the present invention preferably has a water content of 5% by mass or less based on the total mass of the solvent from the viewpoints of suppressing coating defects during coating and improving storage stability. ..
The content of the water is preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.1% by mass or less.
Moreover, the content of the said water may be 0 mass%.
窒素原子を有しない溶剤としては、上述のエステル類、エーテル類、ケトン類、芳香族炭化水素類、及び、スルホキシド類が挙げられる。これらの中でも、乳酸エチル、γ-ブチロラクトン、ジメチルスルホキシド、シクロペンタノン、プロピレングリコールモノメチルエーテルアセテート(PGMEA)、プロピレングリコールモノメチルエーテル(PGME)、3-メトキシブチルアセテート(3-MBA)、メチル-3-メトキシプロピオネート(MMP)、エチルピルべート(ピルビン酸エチル、EP)、2-エトキシエチルアセテート(EA)、n-ブチルアセテート(BA)、又は、プロピレングリコールモノプロピルエーテル(PGP)が好ましく挙げられる。
本発明の硬化性樹脂組成物が、窒素原子を含まない溶剤を含む場合、硬化性樹脂組成物に含まれる溶剤の全質量に対する窒素原子を含まない溶剤の含有量は、10~100質量%であることが好ましく、20~100質量%であることがより好ましく、50~100質量%であることが更に好ましい。
また、本発明の硬化性樹脂組成物は、N-メチルピロリドン等の窒素原子を含む溶剤を実質的に含まない態様とすることもできる。上記態様においては、硬化性樹脂組成物に含まれる溶剤の全質量に対する窒素原子を含む溶剤の含有量は、5質量%以下であることが好ましく、3質量%以下であることがより好ましく、1質量%以下であることが更に好ましく、0.1質量%以下であることが特に好ましい。上記含有量の最小値は、0質量%であってもよい。 The curable resin composition of the present invention preferably contains a solvent containing no nitrogen atom as the solvent. Since dissociation (deprotonation) of a specific compound is likely to occur in a solvent that does not contain nitrogen atoms, the adhesion energy between the specific compound and the metal when the composition is applied to the substrate is likely to increase, and the corrosion suppressing ability is excellent. It is considered easy.
Examples of the solvent having no nitrogen atom include the above-mentioned esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides. Among these, ethyl lactate, γ-butyrolactone, dimethylsulfoxide, cyclopentanone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 3-methoxybutyl acetate (3-MBA), methyl-3- Methoxypropionate (MMP), ethyl pyruvate (ethyl pyruvate, EP), 2-ethoxyethyl acetate (EA), n-butyl acetate (BA), or propylene glycol monopropyl ether (PGP) are preferred. Be done.
When the curable resin composition of the present invention contains a solvent containing no nitrogen atom, the content of the solvent containing no nitrogen atom with respect to the total mass of the solvent contained in the curable resin composition is 10 to 100% by mass. It is preferably 20 to 100% by mass, more preferably 50 to 100% by mass.
Further, the curable resin composition of the present invention may be in an embodiment that does not substantially contain a solvent containing a nitrogen atom such as N-methylpyrrolidone. In the above aspect, the content of the solvent containing a nitrogen atom with respect to the total mass of the solvent contained in the curable resin composition is preferably 5% by mass or less, more preferably 3% by mass or less, and 1 It is more preferably mass% or less, and particularly preferably 0.1 mass% or less. The minimum value of the content may be 0% by mass.
炭素原子、酸素原子及び水素原子のみから構成される溶剤は、溶剤を構成する原子として炭素原子、酸素原子及び水素原子から選ばれた原子のみを含む溶剤であり、炭素原子及び水素原子のみを含む溶剤であってもよいが、炭素原子、酸素原子及び水素原子を含む溶剤であることが好ましい。
炭素原子、酸素原子及び水素原子のみから構成される溶剤としては、上述のエステル類、エーテル類、ケトン類、芳香族炭化水素類が挙げられる。これらの中でも、乳酸エチル、γ-ブチロラクトン、ジメチルスルホキシド、シクロペンタノン、プロピレングリコールモノメチルエーテルアセテート(PGMEA)、プロピレングリコールモノメチルエーテル(PGME)、3-メトキシブチルアセテート(3-MBA)、メチル-3-メトキシプロピオネート(MMP)、エチルピルべート(ピルビン酸エチル、EP)、2-エトキシエチルアセテート(EA)、n-ブチルアセテート(BA)、又は、プロピレングリコールモノプロピルエーテル(PGP)が好ましく挙げられる。
本発明の硬化性樹脂組成物が、炭素原子、酸素原子及び水素原子のみから構成される溶剤を含む場合、硬化性樹脂組成物に含まれる溶剤の全質量に対する炭素原子、酸素原子及び水素原子のみから構成される溶剤の含有量は、10~100質量%であることが好ましく、20~100質量%であることがより好ましく、50~100質量%であることが更に好ましい。
また、本発明の硬化性樹脂組成物は、炭素原子、酸素原子及び水素原子以外の原子を含む溶剤を実質的に含まない態様とすることもできる。上記態様においては、硬化性樹脂組成物に含まれる溶剤の全質量に対する炭素原子、酸素原子及び水素原子以外の原子を含む溶剤の含有量は、5質量%以下であることが好ましく、3質量%以下であることがより好ましく、1質量%以下であることが更に好ましく、0.1質量%以下であることが特に好ましい。上記含有量の最小値は、0質量%であってもよい。 The curable resin composition of the present invention preferably contains as a solvent a solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms.
A solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms is a solvent containing only atoms selected from carbon atoms, oxygen atoms and hydrogen atoms as atoms constituting the solvent, and contains only carbon atoms and hydrogen atoms. It may be a solvent, but a solvent containing a carbon atom, an oxygen atom and a hydrogen atom is preferable.
Examples of the solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms include the above-mentioned esters, ethers, ketones and aromatic hydrocarbons. Among these, ethyl lactate, γ-butyrolactone, dimethylsulfoxide, cyclopentanone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 3-methoxybutyl acetate (3-MBA), methyl-3- Methoxypropionate (MMP), ethyl pyruvate (ethyl pyruvate, EP), 2-ethoxyethyl acetate (EA), n-butyl acetate (BA), or propylene glycol monopropyl ether (PGP) are preferred. Be done.
When the curable resin composition of the present invention contains a solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms, only carbon atoms, oxygen atoms and hydrogen atoms with respect to the total mass of the solvent contained in the curable resin composition The content of the solvent composed of is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and further preferably 50 to 100% by mass.
Further, the curable resin composition of the present invention may be in a mode that substantially does not contain a solvent containing atoms other than carbon atoms, oxygen atoms and hydrogen atoms. In the above aspect, the content of the solvent containing atoms other than carbon atom, oxygen atom and hydrogen atom with respect to the total mass of the solvent contained in the curable resin composition is preferably 5% by mass or less, preferably 3% by mass. It is more preferably less than or equal to, more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. The minimum value of the content may be 0% by mass.
本発明の硬化性樹脂組成物は、溶剤を1種のみ含有していてもよいし、2種以上含有していてもよい。溶剤を2種以上含有する場合は、その合計が上記範囲であることが好ましい。 From the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the curable resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferable that the amount is 10 to 70% by mass, and more preferably 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness and coating method.
The curable 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.
本発明の硬化性樹脂組成物は、pH調整剤を更に含んでもよい。
pH調整剤としては、酸性化合物又は塩基性化合物が挙げられる。
本発明の硬化性樹脂組成物が、酸性化合物、及び、塩基性化合物よりなる群から選ばれた少なくとも一方を含むことにより、組成物又は硬化膜の外界から酸や塩基が入ってきた場合であっても、これらの化合物による緩衝作用により、組成物又は硬化膜のpHが7未満に保たれやすくなり、金属腐食抑制性及び組成物の液保存安定性が向上しやすくなると考えられる。 <pH adjuster>
The curable resin composition of the present invention may further contain a pH adjuster.
Examples of the pH adjuster include acidic compounds and basic compounds.
When the curable resin composition of the present invention contains at least one selected from the group consisting of an acidic compound and a basic compound, so that an acid or a base enters from the outside of the composition or the cured film. However, it is considered that the buffering action of these compounds makes it easier for the pH of the composition or the cured film to be kept below 7, and makes it easier to improve the metal corrosion inhibitory property and the liquid storage stability of the composition.
酸性化合物としては、カルボキシ基を有する化合物が挙げられる。
カルボキシ基を有する化合物としては、特に限定されないが、後述するカルボキシ基を有するシランカップリング剤、又は、ポリアミノカルボン酸化合物又はその塩が好ましい。
ポリアミノカルボン酸化合物又はその塩としては、特に限定されないが、エチレンジアミン四酢酸、トランス-1,2シクロヘキサンジアミン四酢酸、グリコールエーテルジアミン四酢酸、ニトリロトリ酢酸、ジエチレントリアミンペンタ酢酸、又は、これらのアミン塩、アンモニウム塩等が挙げられる。 [Acid compound]
Examples of the acidic compound include compounds having a carboxy group.
The compound having a carboxy group is not particularly limited, but a silane coupling agent having a carboxy group, which will be described later, or a polyaminocarboxylic acid compound or a salt thereof is preferable.
The polyaminocarboxylic acid compound or a salt thereof is not particularly limited, but ethylenediaminetetraacetic acid, trans-1,cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, or amine salts thereof, ammonium. Examples include salt.
本発明の硬化性樹脂組成物は、酸性化合物を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。 The content of the acidic compound with respect to the total solid content of the curable resin composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass, and 0. It is more preferably 5 to 6% by mass.
The curable resin composition of the present invention may contain only one type of acidic compound, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.
本発明の硬化性樹脂組成物は、pH調整剤として、塩基性化合物を含むことも好ましい。
塩基性化合物には、上述のトリアゾール構造を有する化合物は含まれないものとする。
金属腐食抑制性及び保存安定性の観点から、塩基性化合物は、後述の熱酸発生剤、光酸発生剤、又は、マイグレーション抑制剤等に該当する化合物であってもよいが、これらに該当しない化合物であることが好ましい。
本発明において、塩基性化合物とは、硬化性樹脂組成物中で塩基性を呈する化合物であれば特に限定されないが、共役酸のDMSO中のpKaが1.0~7.0であることが好ましく、1.5~7.0であることがより好ましく、2.0~7.0であることが更に好ましい。 [Basic compound]
The curable resin composition of the present invention preferably contains a basic compound as a pH adjuster.
The basic compound does not include the above-mentioned compound having a triazole structure.
From the viewpoint of metal corrosion inhibitory property and storage stability, the basic compound may be a compound corresponding to a thermal acid generator, a photoacid generator, a migration inhibitor, etc., which will be described later, but it does not correspond to these. It is preferably a compound.
In the present invention, the basic compound is not particularly limited as long as it is a compound exhibiting basicity in the curable resin composition, but the pKa of the conjugate acid in DMSO is preferably 1.0 to 7.0. , 1.5 to 7.0, more preferably 2.0 to 7.0.
芳香族アミン構造としては、下記式(A-1)により表される構造が好ましく挙げられる。
式(A-1)中、*はそれぞれ独立に、水素原子又は置換基との結合部位を表し、*のうち少なくとも1つは置換基との結合部位を表す。
式(A-1)中、*はいずれも置換基との結合部位を表すことが好ましい。
また、式(A-1)中、ベンゼン環は、本発明の効果が得られる範囲内において公知の置換基又は縮合環を有していてもよい。 In the present specification, the aromatic amine structure means a structure in which an amino group or a substituted amino group is directly bonded to an aromatic ring, and a structure in which a substituted amino group is bonded to an aromatic ring is preferable, and the aromatic ring is disubstituted. It is more preferable that the structure has an amino group bonded thereto. The substituent in the substituted amino group or the disubstituted amino group is not particularly limited, but a hydrocarbon group which may have a substituent is preferable, and a hydrocarbon group which has at least an alcoholic hydroxyl group as a substituent is preferable. As the hydrocarbon group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is further preferable. The substituents in the disubstituted amino group may be the same or different.
As the aromatic amine structure, a structure represented by the following formula (A-1) is preferably mentioned.
In formula (A-1), * independently represents a binding site with a hydrogen atom or a substituent, and at least one of * represents a binding site with a substituent.
In the formula (A-1), it is preferable that * represents a binding site with a substituent.
Further, in the formula (A-1), the benzene ring may have a known substituent or condensed ring within the range in which the effect of the present invention can be obtained.
本発明における塩基性化合物がアルコール性水酸基を有する場合、塩基性化合物はアルコール性水酸基を有するアミン化合物であることが好ましく、塩基性化合物を有する芳香族アミン化合物であることがより好ましい。
また、上記アミン化合物は、第三級アミン化合物であることが好ましく、第三級芳香族アミン化合物であることがより好ましい。 In the present specification, the alcoholic hydroxyl group means a hydroxy group directly bonded to a carbon atom that is not a ring member of an aromatic ring, and is preferably a hydroxy group directly bonded to a carbon atom contained in an aliphatic hydrocarbon group. ..
When the basic compound in the present invention has an alcoholic hydroxyl group, the basic compound is preferably an amine compound having an alcoholic hydroxyl group, and more preferably an aromatic amine compound having a basic compound.
Further, the amine compound is preferably a tertiary amine compound, and more preferably a tertiary aromatic amine compound.
これらの中でも、芳香族アミン構造及びアルコール性水酸基を含む化合物として、N-フェニル-N’-エチルエタノールアミン、N-フェニルジエタノールアミン、N-p-トリルジエタノールアミン、又は、N-フェニルエタノールアミンが好ましい。 Examples of the compound containing at least one structure selected from the group consisting of an aromatic amine structure and an alcoholic hydroxyl group include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, and 2,5-bis (4'-diethylaminobenzal). ) Cyclopentane, 2,6-bis (4'-diethylaminobenzal) cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-Bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylamino) Phenylbinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) isonaftthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone , 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3 -Methenylcarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4- Morphorinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2-( p-Dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3 ', 4'-Dimethylacetanilide and the like can be mentioned.
Among these, as the compound containing an aromatic amine structure and an alcoholic hydroxyl group, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, or N-phenylethanolamine is preferable.
本発明の硬化性樹脂組成物は、塩基性化合物を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。 The content of the basic compound with respect to the total solid content of the curable resin composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass, and 0. It is more preferably .5 to 6% by mass.
The curable resin composition of the present invention may contain only one type of basic compound, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.
本発明の硬化性樹脂組成物は、シランカップリング剤を含むことが好ましい。
また、本発明の硬化性樹脂組成物は、シランカップリング剤として、カルボキシ基を有するシランカップリング剤を有することが好ましい。
上記カルボキシ基を有するシランカップリング剤は、上述の酸性化合物に該当する。 <Silane coupling agent>
The curable resin composition of the present invention preferably contains a silane coupling agent.
Further, the curable resin composition of the present invention preferably has a silane coupling agent having a carboxy group as the silane coupling agent.
The silane coupling agent having a carboxy group corresponds to the above-mentioned acidic compound.
カルボキシ基を有するシランカップリング剤としては、特に限定されないが、モノアルコキシシリル基、ジアルコキシシリル基又はトリアルコキシシリル基と、カルボキシ基とを有する化合物が好ましく、ジアルコキシシリル基又はトリアルコキシシリル基と、カルボキシ基とを有する化合物がより好ましく、トリアルコキシシリル基と、カルボキシ基とを有する化合物が更に好ましい。
上記モノアルコキシシリル基、上記ジアルコキシシリル基又は上記トリアルコキシシリル基におけるアルコキシ基は特に限定されないが、炭素数1~4のアルコキシ基であることが好ましく、メトキシ基又はエトキシ基がより好ましい。 [Silane coupling agent having a carboxy group]
The silane coupling agent having a carboxy group is not particularly limited, but a compound having a monoalkoxysilyl group, a dialkoxysilyl group or a trialkoxysilyl group and a carboxy group is preferable, and a dialkoxysilyl group or a trialkoxysilyl group And a compound having a carboxy group is more preferable, and a compound having a trialkoxysilyl group and a carboxy group is further preferable.
The alkoxy group in the monoalkoxysilyl group, the dialkoxysilyl group or the trialkoxysilyl group is not particularly limited, but is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.
1gのカルボキシ基を有するシランカップリング剤における、カルボキシ基のモル量(mmol/g)は、3.12~12.5mmol/gであることが好ましく、3.12~6.25mmol/gであることがより好ましい。 The number of carboxy groups in the silane coupling agent having a carboxy group may be 1 or more, but is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
The molar amount (mmol / g) of the carboxy group in the silane coupling agent having 1 g of the carboxy group is preferably 3.12 to 12.5 mmol / g, and is 3.12 to 6.25 mmol / g. Is more preferable.
上記式中、Rはメチル基又はエチル基を表す。 Specific examples of the silane coupling agent having a carboxy group include, but are not limited to, the following compounds.
In the above formula, R represents a methyl group or an ethyl group.
また、カルボキシ基を有するシランカップリング剤の含有量は、硬化性樹脂組成物に含まれる上記塩基性化合物の全質量に対して、5~80質量%であることが好ましく、10~70質量%であることがより好ましい。
本発明の硬化性樹脂組成物は、カルボキシ基を有するシランカップリング剤を1種のみ含有していてもよいし、2種以上含有していてもよい。カルボキシ基を有するシランカップリング剤を2種以上含有する場合は、その合計が上記範囲であることが好ましい。 The content of the silane coupling agent having a carboxy group is preferably 0.1% by mass to 20% by mass, and 0.2% by mass to 10% by mass, based on the total solid content of the curable resin composition. It is preferably 0.5 to 5% by mass, and more preferably 0.5 to 5% by mass.
The content of the silane coupling agent having a carboxy group is preferably 5 to 80% by mass, preferably 10 to 70% by mass, based on the total mass of the basic compound contained in the curable resin composition. Is more preferable.
The curable resin composition of the present invention may contain only one type of silane coupling agent having a carboxy group, or may contain two or more types. When two or more kinds of silane coupling agents having a carboxy group are contained, the total is preferably in the above range.
基材との密着性等の観点からは、本発明の硬化性樹脂組成物は、カルボキシ基を有しない、他のシランカップリング剤を含んでもよい。
他のシランカップリング剤としては、例えば、エポキシ基、オキセタニル基等の環状エーテル基、ビニル基、アリル基、メタクリロイル基等のエチレン性不飽和結合を有する基、アミノ基、ヒドロキシ基、メルカプト基、イミダゾール構造等の含窒素芳香族複素環基、アルキルアミド基等を有するシランカップリング剤が挙げられる。
また、他のシランカップリング剤として、国際公開第2015/199219号の段落0167に記載の化合物、特開2014-191002号公報の段落0062~0073に記載の化合物、国際公開第2011/080992号の段落0063~0071に記載の化合物、特開2014-191252号公報の段落0060~0061に記載の化合物、特開2014-041264号公報の段落0045~0052に記載の化合物、国際公開第2014/097594号の段落0055に記載の化合物のうち、カルボキシ基を有しない化合物が挙げられる。また、特開2011-128358号公報の段落0050~0058に記載のように異なる2種以上のシランカップリング剤を用いることも好ましい。 [Other silane coupling agents]
From the viewpoint of adhesion to the base material and the like, the curable resin composition of the present invention may contain another silane coupling agent having no carboxy group.
Examples of other silane coupling agents include cyclic ether groups such as epoxy group and oxetanyl group, groups having an ethylenically unsaturated bond such as vinyl group, allyl group and methacryloyl group, amino group, hydroxy group and mercapto group. Examples thereof include a silane coupling agent having a nitrogen-containing aromatic heterocyclic group such as an imidazole structure and an alkylamide group.
Further, as other silane coupling agents, the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, and International Publication No. 2011/080992. Compounds described in paragraphs 0063 to 0071, compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/0975994. Among the compounds described in paragraph 0055 of the above, compounds having no carboxy group can be mentioned. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A.
本発明の硬化性樹脂組成物は、他のシランカップリング剤を1種のみ含有していてもよいし、2種以上含有していてもよい。他のシランカップリング剤を2種以上含有する場合は、その合計が上記範囲であることが好ましい。 When the curable resin composition of the present invention contains another silane coupling agent, it is preferably 0.1% by mass to 20% by mass, preferably 0.2% by mass, based on the total solid content of the curable resin composition. It is preferably from mass% to 10% by mass, and more preferably from 0.5 to 5% by mass.
The curable resin composition of the present invention may contain only one type of other silane coupling agent, or may contain two or more types. When two or more other silane coupling agents are contained, the total is preferably in the above range.
本発明の組成物は、上述した特定樹脂以外に、特定樹脂とは異なる、他の樹脂(以下、単に「他の樹脂」ともいう。)を更に含んでもよい。
他の樹脂としては、ポリアミドイミド、ポリアミドイミド前駆体、フェノール樹脂、ポリアミド、エポキシ樹脂、ポリシロキサン、シロキサン構造を含む樹脂、アクリル樹脂等が挙げられる。
例えば、アクリル樹脂を更に加えることにより、塗布性に優れた組成物が得られ、また、耐溶剤性に優れた有機膜が得られる。
例えば、後述する重合性化合物に代えて、又は、後述する重合性化合物に加えて、重量平均分子量が20,000以下の重合性基価の高いアクリル系樹脂を組成物に添加することにより、組成物の塗布性、有機膜の耐溶剤性等を向上させることができる。 <Other resins>
In addition to the above-mentioned specific resin, the composition of the present invention may further contain another resin (hereinafter, also simply referred to as “other resin”) different from the specific resin.
Examples of other resins include polyamide-imide, polyamide-imide precursor, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, and acrylic resin.
For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, and an organic film having excellent solvent resistance can be obtained.
For example, the composition is formed by adding an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable base value to the composition in place of the polymerizable compound described later or in addition to the polymerizable compound described later. It is possible to improve the coatability of an object, the solvent resistance of an organic film, and the like.
また、本発明の組成物における、他の樹脂の含有量は、組成物の全固形分に対し、80質量%以下であることが好ましく、75質量%以下であることがより好ましく、70質量%以下であることが更に好ましく、60質量%以下であることが一層好ましく、50質量%以下であることがより一層好ましい。
また、本発明の組成物の好ましい一態様として、他の樹脂の含有量が低含有量である態様とすることもできる。上記態様において、他の樹脂の含有量は、組成物の全固形分に対し、20質量%以下であることが好ましく、15質量%以下であることがより好ましく、10質量%以下であることが更に好ましく、5質量%以下であることが一層好ましく、1質量%以下であることがより一層好ましい。上記含有量の下限は特に限定されず、0質量%以上であればよい。
本発明の組成物は、他の樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。 When the composition of the present invention contains another resin, 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 composition. More preferably, it is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more. ..
The content of the other resin in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass, based on the total solid content of the composition. It is more preferably less than or equal to, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
Further, as a preferable aspect of the composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and preferably 10% by mass or less, based on the total solid content of the composition. More preferably, it is more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.
本発明の組成物は、感光剤を含む。
感光剤としては、光重合開始剤が好ましい。 <Photosensitizer>
The composition of the present invention contains a photosensitizer.
As the photosensitizer, a photopolymerization initiator is preferable.
本発明の組成物は、感光剤として、光重合開始剤を含むことが好ましい。
光重合開始剤は、光ラジカル重合開始剤であることが好ましい。光ラジカル重合開始剤としては、特に制限はなく、公知の光ラジカル重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する光ラジカル重合開始剤が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよい。 [Photopolymerization initiator]
The composition of the present invention preferably contains a photopolymerization initiator as the photosensitizer.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
ここで、ラジカル重合開始能を有するとは、ラジカル重合を開始させることのできるフリーラジカルを発生させることができることを意味する。例えば、ラジカル重合性モノマーとバインダーポリマーと金属元素含有化合物とを含む組成物に対して、金属元素含有化合物が光を吸収する波長域であって、ラジカル重合性モノマーが光を吸収しない波長域の光を照射した時に、ラジカル重合性モノマーの消失の有無を確認することにより重合開始能の有無を確認することができる。消失の有無を確認するには、ラジカル重合性モノマーやバインダーポリマーの種類に応じて適宜の方法を選択できるが、例えばIR測定(赤外分光測定)又はHPLC測定(高速液体クロマトグラフィ)により確認すればよい。 From the viewpoint of facilitating the satisfaction of at least one formula selected from the group consisting of the above formulas (1) and (2) in the organic film, the composition of the present invention will be described later as a photoradical polymerization initiator. It preferably contains a metal element-containing compound. That is, in the present invention, among the metal element-containing compounds described later, those having a radical polymerization initiatoring ability can be used as a photoradical polymerization initiator.
Here, having the ability to initiate radical polymerization means that free radicals capable of initiating radical polymerization can be generated. For example, with respect to a composition containing a radically polymerizable monomer, a binder polymer, and a metal element-containing compound, a wavelength range in which the metal element-containing compound absorbs light and the radically polymerizable monomer does not absorb light. The presence or absence of the polymerization initiation ability can be confirmed by confirming the presence or absence of the disappearance of the radically polymerizable monomer when irradiated with light. In order to confirm the presence or absence of disappearance, an appropriate method can be selected depending on the type of radical polymerizable monomer or binder polymer, but for example, it can be confirmed by IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography). Good.
また、本発明の組成物が、ラジカル重合開始能を有する金属元素含有化合物等を含む場合、本発明の組成物が、上記金属元素含有化合物と、他の光ラジカル重合開始剤とを含むことも好ましい。
本発明の組成物において、金属元素含有化合物と、他の光ラジカル重合開始剤とを含む場合、金属元素含有化合物と、他の光ラジカル重合開始剤の合計含有量に対する、金属元素含有化合物の含有量は、20~80質量%であることが好ましく、30~70質量%であることがより好ましい。
また、上記他の光ラジカル重合開始剤としては、後述のオキシム化合物が好ましい。 When the composition of the present invention contains a metal element-containing compound or the like having a radical polymerization initiating ability, it is also preferable that the composition of the present invention does not substantially contain a radical polymerization initiator other than the above-mentioned metal element-containing compound. The fact that the composition of the present invention does not substantially contain a radical polymerization initiator other than the metal element-containing compound means that the content of the radical polymerization initiator other than the metal element-containing compound is the metal element-containing compound. It is said that it is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.1% by mass, based on the total mass of the above.
Further, when the composition of the present invention contains a metal element-containing compound or the like having a radical polymerization initiation ability, the composition of the present invention may contain the metal element-containing compound and another photoradical polymerization initiator. preferable.
When the composition of the present invention contains a metal element-containing compound and another photoradical polymerization initiator, the content of the metal element-containing compound relative to the total content of the metal element-containing compound and the other photoradical polymerization initiator. The amount is preferably 20 to 80% by mass, more preferably 30 to 70% by mass.
Further, as the above-mentioned other photoradical polymerization initiator, an oxime compound described later is preferable.
また、本発明の組成物は、感光剤として、光酸発生剤を含むことも好ましい。
光酸発生剤を含有することで、例えば、組成物層の露光部に酸が発生して、上記露光部の現像液(例えば、アルカリ水溶液)に対する溶解性が増大し、露光部が現像液により除去されるポジ型のパターンを得ることができる。
また、組成物が、光酸発生剤と、後述するラジカル重合性化合物以外の重合性化合物とを含有することにより、例えば、露光部に発生した酸により上記重合性化合物の架橋反応が促進され、露光部が非露光部よりも現像液により除去されにくくなる態様とすることもできる。このような態様によれば、ネガ型のパターンを得ることができる。 [Photoacid generator]
Further, the composition of the present invention preferably contains a photoacid generator as a photosensitizer.
By containing the photoacid generator, for example, acid is generated in the exposed portion of the composition layer, the solubility of the exposed portion in the developing solution (for example, an alkaline aqueous solution) is increased, and the exposed portion is affected by the developing solution. A positive pattern to be removed can be obtained.
Further, when the composition contains a photoacid generator and a polymerizable compound other than the radically polymerizable compound described later, for example, the acid generated in the exposed portion promotes the cross-linking reaction of the polymerizable compound. The exposed portion may be more difficult to be removed by the developing solution than the non-exposed portion. According to such an aspect, a negative type pattern can be obtained.
上記ナフトキノンジアジド化合物としては、例えば、1,2-ナフトキノン-2-ジアジド-5-スルホン酸又は1,2-ナフトキノン-2-ジアジド-4-スルホン酸、これらの化合物の塩又はエステル化合物等が挙げられる。 The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinone diazido sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.
Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds of these compounds. Be done.
オキシムスルホネート化合物は、オキシムスルホネート基を有していれば特に制限はないが、下記式(OS-1)、後述する式(OS-103)、式(OS-104)、又は、式(OS-105)で表されるオキシムスルホネート化合物であることが好ましい。 The photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as “oxime sulfonate compound”).
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-) It is preferably an oxime sulfonate compound represented by 105).
式(OS-1)中、m3は、0~3の整数を表し、0又は1が好ましい。m3が2又は3であるとき、複数のX3は同一でも異なっていてもよい。
式(OS-1)中、R34は、アルキル基又はアリール基を表し、炭素数1~10のアルキル基、炭素数1~10のアルコキシル基、炭素数1~5のハロゲン化アルキル基、炭素数1~5のハロゲン化アルコキシル基、Wで置換されていてもよいフェニル基、Wで置換されていてもよいナフチル基又はWで置換されていてもよいアントラニル基であることが好ましい。Wは、ハロゲン原子、シアノ基、ニトロ基、炭素数1~10のアルキル基、炭素数1~10のアルコキシル基、炭素数1~5のハロゲン化アルキル基又は炭素数1~5のハロゲン化アルコキシル基、炭素数6~20のアリール基、炭素数6~20のハロゲン化アリール基を表す。 Wherein (OS-1), X 3 is an alkyl group, an alkoxyl group, or a halogen atom. If X 3 there are a plurality, each be the same or may be different. Alkyl group and an alkoxyl group represented by X 3 may have a substituent. The alkyl group in the above X 3, 1 to 4 carbon atoms, straight-chain or branched alkyl group is preferable. The alkoxyl group represented by X 3, preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom in the X 3, a chlorine atom or a fluorine atom is preferable.
In the formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X 3 may be the same or different.
In the formula (OS-1), R 34 represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxyl group of numbers 1 to 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W or an anthranyl group optionally substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxyl halide having 1 to 5 carbon atoms. It represents a group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.
式(OS-103)~式(OS-105)中、Rs1で表されるアルキル基(炭素数1~30が好ましい)、アリール基(炭素数6~30が好ましい)又はヘテロアリール基(炭素数4~30が好ましい)は、置換基Tを有していてもよい。 In formulas (OS-103) to (OS-105), R s1 represents an alkyl group, an aryl group or a heteroaryl group, and R s2, which may be present in a plurality of R s2, independently represents a hydrogen atom, an alkyl group and an aryl group. R s6 , which represents a group or a halogen atom and may be present in a plurality, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and Xs represents O or S. Represented, ns represents 1 or 2, ms represents an integer from 0 to 6.
In formulas (OS-103) to (OS-105), an alkyl group represented by R s1 (preferably having 1 to 30 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms) or a heteroaryl group (carbon). (Preferably numbers 4 to 30) may have a substituent T.
式(OS-103)、式(OS-104)、又は、式(OS-105)中、XsはO又はSを表し、Oであることが好ましい。上記式(OS-103)~(OS-105)において、Xsを環員として含む環は、5員環又は6員環である。 In formulas (OS-103) to (OS-105), R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms). , Hydrogen atom or alkyl group is more preferable. Of the R s2 that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom. The alkyl group or aryl group represented by R s2 may have a substituent T.
In the formula (OS-103), the formula (OS-104), or the formula (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
式(OS-103)~式(OS-105)中、Rs6で表されるアルキル基(炭素数1~30が好ましい)及びアルキルオキシ基(炭素数1~30が好ましい)は、置換基を有していてもよい。
式(OS-103)~式(OS-105)中、msは0~6の整数を表し、0~2の整数であることが好ましく、0又は1であることがより好ましく、0であることが特に好ましい。 In formulas (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
In formulas (OS-103) to (OS-105), the alkyl group represented by R s6 (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) are substituents. You may have.
In the formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.
式(OS-106)~式(OS-111)中、Rt7は、水素原子又は臭素原子を表し、水素原子であることが好ましい。 In formulas (OS-106) to (OS-111), R t1 represents an alkyl group, an aryl group or a heteroaryl group, R t7 represents a hydrogen atom or a bromine atom, and R t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups, R t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups, and R t2 represents a hydrogen atom or a methyl group.
In formulas (OS-106) to (OS-111), R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
Rt2は、水素原子又はメチル基を表し、水素原子であることが好ましい。
また、上記オキシムスルホネート化合物において、オキシムの立体構造(E,Z)については、いずれか一方であっても、混合物であってもよい。
上記式(OS-103)~式(OS-105)で表されるオキシムスルホネート化合物の具体例としては、特開2011-209692号公報の段落番号0088~0095、特開2015-194674号公報の段落番号0168~0194に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。 In formulas (OS-106) to (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692A and paragraphs of JP2015-194674A. The compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.
式(OS-101)又は式(OS-102)中、Ru2aは、アルキル基又はアリール基を表す。
式(OS-101)又は式(OS-102)中、Xuは、-O-、-S-、-NH-、-NRu5-、-CH2-、-CRu6H-又はCRu6Ru7-を表し、Ru5~Ru7はそれぞれ独立に、アルキル基又はアリール基を表す。 In formula (OS-101) or formula (OS-102), Ru9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Represents an aryl group or a heteroaryl group. The embodiment in which R u9 is a cyano group or an aryl group is more preferable, and the embodiment in which R u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
In formula (OS-101) or formula (OS-102), Ru2a represents an alkyl or aryl group.
In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH- , -NR u5-, -CH 2- , -CR u6 H- or CR u6 R u7. Represents −, and R u5 to R u7 independently represent an alkyl group or an aryl group.
また、上記オキシムスルホネート化合物において、オキシムやベンゾチアゾール環の立体構造(E,Z等)についてはそれぞれ、いずれか一方であっても、混合物であってもよい。
式(OS-101)で表される化合物の具体例としては、特開2011-209692号公報の段落番号0102~0106、特開2015-194674号公報の段落番号0195~0207に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。
上記化合物の中でも、b-9、b-16、b-31、b-33が好ましい。 The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
Further, in the oxime sulfonate compound, the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraph numbers 0102 to 0106 of JP2011-209692 and paragraph numbers 0195 to 0207 of JP2015-194674. These contents are incorporated herein by reference.
Among the above compounds, b-9, b-16, b-31, and b-33 are preferable.
より好適には、少なくとも一つのモノ、ジ、又はトリハロゲン置換メチル基がs-トリアジン環に結合したs-トリアジン誘導体、具体的には、例えば、2,4,6-トリス(モノクロロメチル)-s-トリアジン、2,4,6-トリス(ジクロロメチル)-s-トリアジン、2,4,6-トリス(トリクロロメチル)-s-トリアジン、2-メチル-4,6-ビス(トリクロロメチル)-s-トリアジン、2―n-プロピル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(α,α,β-トリクロロエチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-フェニル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-メトキシフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(3,4-エポキシフェニル)-4、6-ビス(トリクロロメチル)-s-トリアジン、2-(p-クロロフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-〔1-(p-メトキシフェニル)-2,4-ブタジエニル〕-4,6-ビス(トリクロロメチル)-s-トリアジン、2-スチリル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-メトキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-i-プロピルオキシスチリル)-4、6-ビス(トリクロロメチル)-s-トリアジン、2-(p-トリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-ナトキシナフチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-フェニルチオ-4,6-ビス(トリクロロメチル)-s-トリアジン、2-ベンジルチオ-4,6-ビス(トリクロロメチル)-s-トリアジン、2,4,6-トリス(ジブロモメチル)-s-トリアジン、2,4,6-トリス(トリブロモメチル)-s-トリアジン、2-メチル-4,6-ビス(トリブロモメチル)-s-トリアジン、2-メトキシ-4,6-ビス(トリブロモメチル)-s-トリアジン等が挙げられる。 As the photoacid generator, an organic halogenated compound can also be applied. Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-46-4605, JP-A. 48-36281, JP-A-55-3270, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62- 212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, M.D. P. The compounds described in Hutt “Jurnal of Heterocyclic Chemistry” 1 (No. 3), (1970) and the like can be mentioned, and in particular, an oxazole compound substituted with a trihalomethyl group: an S-triazine compound can be mentioned.
More preferably, an s-triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is attached to the s-triazine ring, specifically, for example 2,4,6-tris (monochromomethyl)- s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine , 2-Phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-Butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine , 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s- Examples thereof include triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like.
式(RI-I)中、Ar11は置換基を1~6有していても良い炭素数20以下のアリール基を表し、好ましい置換基としては炭素数1~12のアルキル基、炭素数1~12のアルケニル基、炭素数1~12のアルキニル基、炭素数1~12のアリール基、炭素数1~12のアルコキシ基、炭素数1~12のアリーロキシ基、ハロゲン原子、炭素数1~12のアルキルアミノ基、炭素数1~12のジアルキルアミノ基、炭素数1~12のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシル基、シアノ基、スルホニル基、炭素数1~12のチオアルキル基、炭素数1~12のチオアリール基が挙げられる。Z11-は1価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオンが好ましい。式(RI-II)中、Ar21、Ar22は各々独立に置換基を1~6有していても良い炭素数20以下のアリール基を表し、好ましい置換基としては炭素数1~12のアルキル基、炭素数1~12のアルケニル基、炭素数1~12のアルキニル基、炭素数1~12のアリール基、炭素数1~12のアルコキシ基、炭素数1~12のアリーロキシ基、ハロゲン原子、炭素数1~12のアルキルアミノ基、炭素数1~12のジアルキルアミノ基、炭素数1~12のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシル基、シアノ基、スルホニル基、炭素数1~12のチオアルキル基、炭素数1~12のチオアリール基が挙げられる。Z21 -は1価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。式(RI-III)中、R31、R32、R33は各々独立に置換基を1~6有していても良い炭素数20以下のアリール基又はアルキル基、アルケニル基、アルキニル基を表し、好ましくは反応性、安定性の面から、アリール基であることが望ましい。好ましい置換基としては炭素数1~12のアルキル基、炭素数1~12のアルケニル基、炭素数1~12のアルキニル基、炭素数1~12のアリール基、炭素数1~12のアルコキシ基、炭素数1~12のアリーロキシ基、ハロゲン原子、炭素数1~12のアルキルアミノ基、炭素数1~12のジアルキルアミノ基、炭素数1~12のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシル基、シアノ基、スルホニル基、炭素数1~12のチオアルキル基、炭素数1~12のチオアリール基が挙げられる。Z31-は1価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。 Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III).
In the formula (RI-I), Ar 11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 1 carbon atom. ~ 12 alkenyl groups, alkynyl groups with 1 to 12 carbon atoms, aryl groups with 1 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, allyloxy groups with 1 to 12 carbon atoms, halogen atoms, 1 to 12 carbon atoms Alkylamino group, dialkylamino group having 1 to 12 carbon atoms, alkylamide group or arylamide group having 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, Examples thereof include a thioaryl group having 1 to 12 carbon atoms. Z11 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, surface stability Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion are preferable. In the formula (RI-II), Ar 21 and Ar 22 each represent an aryl group having 20 or less carbon atoms which may independently have 1 to 6 substituents, and preferred substituents have 1 to 12 carbon atoms. Alkyl group, alkenyl group with 1 to 12 carbon atoms, alkynyl group with 1 to 12 carbon atoms, aryl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms, aryloxy group with 1 to 12 carbon atoms, halogen atom , Alkylamino group with 1 to 12 carbon atoms, dialkylamino group with 1 to 12 carbon atoms, alkylamide group or arylamide group with 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, 1 carbon number Examples thereof include a thioalkyl group having up to 12 and a thioaryl group having 1 to 12 carbon atoms. Z 21 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, From the viewpoint of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable. In formula (RI-III), R 31 , R 32 , and R 33 each represent an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 20 or less carbon atoms which may independently have 1 to 6 substituents. , Preferably an aryl group from the viewpoint of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. Allyloxy group having 1 to 12 carbon atoms, halogen atom, alkylamino group having 1 to 12 carbon atoms, dialkylamino group having 1 to 12 carbon atoms, alkylamide group or arylamide group having 1 to 12 carbon atoms, carbonyl group, carboxyl Examples thereof include a group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z31 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of properties, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
上記感光剤の含有量は、特定樹脂100質量部に対し1~30質量部であることが好ましく、1~20質量部であることがより好ましく、2~10質量部であることが特に好ましい。
上記特定化合物の含有量は、特定樹脂100質量部に対し、0.1~15質量部であることが好ましく、0.2~10質量部であることがより好ましく、0.5~8質量部であることが特に好ましい。
上記溶剤の含有量は、特定樹脂100質量部に対し、70~250質量部であることが好ましく、80~230質量部であることがより好ましく、100~200質量部であることが特に好ましい。 When the curable resin composition of the present invention contains a photosensitive agent, the curable resin composition of the present invention contains 1 to 40 parts by mass of the photosensitive agent and 0. It is preferable to contain 05 to 20 parts by mass and 50 to 300 parts by mass of the above-mentioned solvent.
The content of the photosensitizer is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 2 to 10 parts by mass with respect to 100 parts by mass of the specific resin.
The content of the specific compound is preferably 0.1 to 15 parts by mass, more preferably 0.2 to 10 parts by mass, and 0.5 to 8 parts by mass with respect to 100 parts by mass of the specific resin. Is particularly preferable.
The content of the solvent is preferably 70 to 250 parts by mass, more preferably 80 to 230 parts by mass, and particularly preferably 100 to 200 parts by mass with respect to 100 parts by mass of the specific resin.
本発明の組成物は、熱重合開始剤を含んでもよく、特に熱ラジカル重合開始剤を含んでもよい。熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性を有する化合物の重合反応を開始又は促進させる化合物である。熱ラジカル重合開始剤を添加することによって、後述する加熱工程において、樹脂及び重合性化合物の重合反応を進行させることもできるので、より耐溶剤性を向上できる。 <Thermal polymerization initiator>
The composition of the present invention may contain a thermal polymerization initiator, and in particular, a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be allowed to proceed in the heating step described later, so that the solvent resistance can be further improved.
本発明の組成物は、熱酸発生剤を含んでもよい。
熱酸発生剤は、加熱により酸を発生し、ヒドロキシメチル基、アルコキシメチル基又はアシルオキシメチル基を有する化合物、エポキシ化合物、オキセタン化合物及びベンゾオキサジン化合物から選ばれる少なくとも1種の化合物の架橋反応を促進させる効果がある。 <Thermal acid generator>
The composition of the present invention may contain a thermoacid generator.
The thermoacid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound. It has the effect of making it.
熱分解開始温度は、熱酸発生剤を耐圧カプセル中5℃/分で500℃まで加熱した場合に、最も温度が低い発熱ピークのピーク温度として求められる。
熱分解開始温度を測定する際に用いられる機器としては、Q2000(TAインスツルメント社製)等が挙げられる。 The thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the composition is applied to the substrate, and during final heating (cure: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
The thermal decomposition start temperature is obtained as the peak temperature of the exothermic peak, which is the lowest temperature when the thermoacid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule.
Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).
本発明の硬化性樹脂組成物は、オニウム塩を更に含んでもよい。
特に、本発明の硬化性樹脂組成物が特定樹脂としてポリイミド前駆体又はポリベンゾオキサゾール前駆体を含む場合、オニウム塩を含むことが好ましい。
オニウム塩の種類等は特に定めるものではないが、アンモニウム塩、イミニウム塩、スルホニウム塩、ヨードニウム塩又はホスホニウム塩が好ましく挙げられる。
これらの中でも、熱安定性が高い観点からはアンモニウム塩又はイミニウム塩が好ましく、ポリマーとの相溶性の観点からはスルホニウム塩、ヨードニウム塩又はホスホニウム塩が好ましい。 <Onium salt>
The curable resin composition of the present invention may further contain an onium salt.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it preferably contains an onium salt.
The type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt and phosphonium salt are preferably mentioned.
Among these, an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability, and a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.
すなわち、オニウム塩は、同一の分子構造内に、カチオン部と、アニオン部と、を有する分子内塩であってもよいし、それぞれ別分子であるカチオン分子と、アニオン分子と、がイオン結合した分子間塩であってもよいが、分子間塩であることが好ましい。また、本発明の硬化性樹脂組成物において、上記カチオン部又はカチオン分子と、上記アニオン部又はアニオン分子と、はイオン結合により結合されていてもよいし、解離していてもよい。
オニウム塩におけるカチオンとしては、アンモニウムカチオン、ピリジニウムカチオン、スルホニウムカチオン、ヨードニウムカチオン又はホスホニウムカチオンが好ましく、テトラアルキルアンモニウムカチオン、スルホニウムカチオン及びヨードニウムカチオンよりなる群から選択される少なくとも1種のカチオンがより好ましい。 The onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bonded via a covalent bond. ..
That is, the onium salt may be an intramolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are separate molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the curable resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
As the cation in the onium salt, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.
熱塩基発生剤とは、加熱により塩基を発生する化合物をいい、例えば、40℃以上に加熱すると塩基を発生する化合物等が挙げられる。 The onium salt used in the present invention may be a thermobase generator described later.
The thermal base generator refers to a compound that generates a base by heating, and examples thereof include a compound that generates a base when heated to 40 ° C. or higher.
本発明において、アンモニウム塩とは、アンモニウムカチオンと、アニオンとの塩を意味する。 [Ammonium salt]
In the present invention, the ammonium salt means a salt of an ammonium cation and an anion.
アンモニウムカチオンとしては、第四級アンモニウムカチオンが好ましい。
また、アンモニウムカチオンとしては、下記式(101)で表されるカチオンが好ましい。
式(101)中、R1~R4はそれぞれ独立に、水素原子又は炭化水素基を表し、R1~R4の少なくとも2つはそれぞれ結合して環を形成してもよい。 -Ammonium cation-
As the ammonium cation, a quaternary ammonium cation is preferable.
Further, as the ammonium cation, a cation represented by the following formula (101) is preferable.
In formula (101), R 1 to R 4 each independently represent a hydrogen atom or a hydrocarbon group, and at least two of R 1 to R 4 may be bonded to each other to form a ring.
R1~R4の少なくとも2つはそれぞれ結合して環を形成する場合、上記環はヘテロ原子を含んでもよい。上記ヘテロ原子としては、窒素原子が挙げられる。 In the formula (101), R 1 to R 4 are each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms or 6 to 6 carbon atoms. It is more preferably 12 aryl groups. R 1 to R 4 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy. Examples thereof include a carbonyl group and an acyloxy group.
When at least two of R 1 to R 4 are bonded to each other to form a ring, the ring may contain a hetero atom. Examples of the hetero atom include a nitrogen atom.
式(Y1-1)において、R101は、脂肪族炭化水素、芳香族炭化水素、又は、これらが結合した構造からn個の水素原子を除いた基であることが好ましく、炭素数2~30の飽和脂肪族炭化水素、ベンゼン又はナフタレンからn個の水素原子を除いた基であることがより好ましい。
式(Y1-1)において、nは1~4であることが好ましく、1又は2であることがより好ましく、1であることが更に好ましい。
式(Y1-2)において、Ar101及びAr102はそれぞれ独立に、フェニル基又はナフチル基であることが好ましく、フェニル基がより好ましい。 In the formula (Y1-1) and (Y1-2), R 101 represents an n-valent organic group, R 1 has the same meaning as R 1 in the formula (101), Ar 101 and Ar 102 are each independently , Represents an aryl group, and n represents an integer of 1 or more.
In the formula (Y1-1), R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
In the formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In the formula (Y1-2), Ar 101 and Ar 102 are preferably phenyl groups or naphthyl groups, respectively, and more preferably phenyl groups.
アンモニウム塩におけるアニオンとしては、カルボン酸アニオン、フェノールアニオン、リン酸アニオン及び硫酸アニオンから選ばれる1種が好ましく、塩の安定性と熱分解性を両立させられるという理由からカルボン酸アニオンがより好ましい。すなわち、アンモニウム塩は、アンモニウムカチオンとカルボン酸アニオンとの塩がより好ましい。
カルボン酸アニオンは、2個以上のカルボキシ基を持つ2価以上のカルボン酸のアニオンが好ましく、2価のカルボン酸のアニオンがより好ましい。この態様によれば、硬化性樹脂組成物の安定性、硬化性及び現像性をより向上できる。特に、2価のカルボン酸のアニオンを用いることで、硬化性樹脂組成物の安定性、硬化性及び現像性を更に向上できる。 -Anion-
As the anion in the ammonium salt, one selected from a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfuric acid anion is preferable, and a carboxylic acid anion is more preferable because both salt stability and thermodegradability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
The carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxy groups, and more preferably a divalent carboxylic acid anion. According to this aspect, the stability, curability and developability of the curable resin composition can be further improved. In particular, by using a divalent carboxylic acid anion, the stability, curability and developability of the curable resin composition can be further improved.
式(X1)において、EWGは、電子求引性基を表す。 The carboxylic acid anion is preferably represented by the following formula (X1).
In formula (X1), EWG represents an electron-attracting group.
σmが正の値を示す置換基の例としては、CF3基(σm=0.43)、CF3C(=O)基(σm=0.63)、HC≡C基(σm=0.21)、CH2=CH基(σm=0.06)、Ac基(σm=0.38)、MeOC(=O)基(σm=0.37)、MeC(=O)CH=CH基(σm=0.21)、PhC(=O)基(σm=0.34)、H2NC(=O)CH2基(σm=0.06)などが挙げられる。なお、Meはメチル基を表し、Acはアセチル基を表し、Phはフェニル基を表す(以下、同じ)。 In the present embodiment, the electron-attracting group means that Hammett's substituent constant σm shows a positive value. Here, σm is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642. The electron-attracting group in the present embodiment is not limited to the substituent described in the above document.
Examples of substituents in which σm shows a positive value are CF 3 groups (σm = 0.43), CF 3 C (= O) groups (σm = 0.63), and HC≡C groups (σm = 0. 21), CH 2 = CH group (σm = 0.06), Ac group (σm = 0.38), MeOC (= O) group (σm = 0.37), MeC (= O) CH = CH group ( σm = 0.21), PhC (= O) group (σm = 0.34), H 2 NC (= O) CH 2 group (σm = 0.06) and the like. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same applies).
式(EWG-1)~(EWG-6)中、Rx1~Rx3は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基、ヒドロキシ基又はカルボキシ基を表し、Arは芳香族基を表す。 The EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
In the formulas (EWG-1) to (EWG-6), R x1 to R x3 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group or a carboxy group, and Ar is an aromatic group. Represents.
式(XA)において、L10は、単結合、又は、アルキレン基、アルケニレン基、芳香族基、-NRX-及びこれらの組み合わせよりなる群から選ばれる2価の連結基を表し、RXは、水素原子、アルキル基、アルケニル基又はアリール基を表す。 In the present invention, the carboxylic acid anion is preferably represented by the following formula (XA).
In the formula (XA), L 10 represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR X - represents and divalent connecting group selected from the group consisting a combination thereof, R X is , Hydrogen atom, alkyl group, alkenyl group or aryl group.
上記pKaの下限は特に限定されないが、発生する塩基が中和されにくく、複素環ポリマー含有前駆体などの環化効率を良好にするという観点からは、-3以上であることが好ましく、-2以上であることがより好ましい。
上記pKaとしては、Determination of Organic Structures by Physical Methods(著者:Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; 編纂:Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955)や、Data for Biochemical Research(著者:Dawson, R.M.C.et al; Oxford, Clarendon Press, 1959)に記載の値を参照することができる。これらの文献に記載の無い化合物については、ACD/pKa(ACD/Labs製)のソフトを用いて構造式より算出した値を用いることとする。 The onium salt in the present invention contains an ammonium cation as a cation from the viewpoint that the cyclization of the heterocyclic polymer-containing precursor is easily performed at a low temperature and the storage stability of the curable resin composition is easily improved. As the salt as an anion, it is preferable to contain an anion having a conjugate acid pKa (pKaH) of 2.5 or less, and more preferably to contain an anion having a pKa (pKaH) of 1.8 or less.
The lower limit of pKa is not particularly limited, but it is preferably -3 or more, preferably -2 or more, from the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of the heterocyclic polymer-containing precursor or the like is improved. The above is more preferable.
The above pKa includes Determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O., Nachod, F.C.; See Nachod, F.C .; Academic Press, New York, 1955) and Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 19). Can be done. For compounds not described in these documents, the values calculated from the structural formulas using software of ACD / pKa (manufactured by ACD / Labs) shall be used.
本発明において、イミニウム塩とは、イミニウムカチオンと、アニオンとの塩を意味する。アニオンとしては、上述のアンモニウム塩におけるアニオンと同様のものが例示され、好ましい態様も同様である。 [Iminium salt]
In the present invention, the iminium salt means a salt of an iminium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
イミニウムカチオンとしては、ピリジニウムカチオンが好ましい。
また、イミニウムカチオンとしては、下記式(102)で表されるカチオンも好ましい。
As the iminium cation, a pyridinium cation is preferable.
Further, as the iminium cation, a cation represented by the following formula (102) is also preferable.
式(102)中、R5及びR6は上述の式(101)におけるR1~R4と同義であり、好ましい態様も同様である。
式(102)中、R7はR5及びR6の少なくとも1つと結合して環を形成することが好ましい。上記環はヘテロ原子を含んでもよい。上記ヘテロ原子としては、窒素原子が挙げられる。また、上記環としてはピリジン環が好ましい。 In formula (102), R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group, R 7 represents a hydrocarbon group, and at least two of R 5 to R 7 are bonded to each other to form a ring. It may be formed.
In the formula (102), R 5 and R 6 are synonymous with R 1 to R 4 in the above formula (101), and the preferred embodiment is also the same.
In formula (102), R 7 preferably combines with at least one of R 5 and R 6 to form a ring. The ring may contain a heteroatom. Examples of the hetero atom include a nitrogen atom. Further, as the ring, a pyridine ring is preferable.
式(Y1-3)~(Y1-5)において、R101は、n価の有機基を表し、R5は式(102)におけるR5と同義であり、R7は式(102)におけるR7と同義であり、n及びmは、1以上の整数を表す。
式(Y1-3)において、R101は、脂肪族炭化水素、芳香族炭化水素、又は、これらが結合した構造からn個の水素原子を除いた基であることが好ましく、炭素数2~30の飽和脂肪族炭化水素、ベンゼン又はナフタレンからn個の水素原子を除いた基であることがより好ましい。
式(Y1-3)において、nは1~4であることが好ましく、1又は2であることがより好ましく、1であることが更に好ましい。
式(Y1-5)において、mは0~4であることが好ましく、1又は2であることがより好ましく、1であることが更に好ましい。 The iminium cation is preferably represented by any of the following formulas (Y1-3) to (Y1-5).
In Formula (Y1-3) ~ (Y1-5), R 101 represents an n-valent organic group, R 5 has the same meaning as R 5 in the formula (102), R 7 is R in the formula (102) Synonymous with 7 , n and m represent integers of 1 or more.
In the formula (Y1-3), R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the structure to which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
In the formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In the formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and even more preferably 1.
本発明において、スルホニウム塩とは、スルホニウムカチオンと、アニオンとの塩を意味する。アニオンとしては、上述のアンモニウム塩におけるアニオンと同様のものが例示され、好ましい態様も同様である。 [Sulfonium salt]
In the present invention, the sulfonium salt means a salt of a sulfonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
スルホニウムカチオンとしては、第三級スルホニウムカチオンが好ましく、トリアリールスルホニウムカチオンがより好ましい。
また、スルホニウムカチオンとしては、下記式(103)で表されるカチオンが好ましい。
As the sulfonium cation, a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable.
Further, as the sulfonium cation, a cation represented by the following formula (103) is preferable.
R8~R10はそれぞれ独立に、アルキル基又はアリール基であることが好ましく、炭素数1~10のアルキル基又は炭素数6~12のアリール基であることがより好ましく、炭素数6~12のアリール基であることが更に好ましく、フェニル基であることが更に好ましい。
R8~R10は置換基を有していてもよく、置換基の例としては、ヒドロキシ基、アリール基、アルコキシ基、アリールオキシ基、アリールカルボニル基、アルキルカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基等が挙げられる。これらの中でも、置換基として、アルキル基、又は、アルコキシ基を有することが好ましく、分岐アルキル基又はアルコキシ基を有することがより好ましく、炭素数3~10の分岐アルキル基、又は、炭素数1~10のアルコキシ基を有することが更に好ましい。
R8~R10は同一の基であっても、異なる基であってもよいが、合成適性上の観点からは、同一の基であることが好ましい。 In formula (103), R 8 to R 10 each independently represent a hydrocarbon group.
R 8 to R 10 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
R 8 to R 10 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy. Examples thereof include a carbonyl group and an acyloxy group. Among these, the substituent preferably has an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and has a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 1 to carbon atoms. It is more preferable to have 10 alkoxy groups.
R 8 to R 10 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
本発明において、ヨードニウム塩とは、ヨードニウムカチオンと、アニオンとの塩を意味する。アニオンとしては、上述のアンモニウム塩におけるアニオンと同様のものが例示され、好ましい態様も同様である。 [Iodonium salt]
In the present invention, the iodonium salt means a salt of an iodonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
ヨードニウムカチオンとしては、ジアリールヨードニウムカチオンが好ましい。
また、ヨードニウムカチオンとしては、下記式(104)で表されるカチオンが好ましい。
As the iodonium cation, a diaryl iodonium cation is preferable.
Further, as the iodonium cation, a cation represented by the following formula (104) is preferable.
R11及びR12はそれぞれ独立に、アルキル基又はアリール基であることが好ましく、炭素数1~10のアルキル基又は炭素数6~12のアリール基であることがより好ましく、炭素数6~12のアリール基であることが更に好ましく、フェニル基であることが更に好ましい。
R11及びR12は置換基を有していてもよく、置換基の例としては、ヒドロキシ基、アリール基、アルコキシ基、アリールオキシ基、アリールカルボニル基、アルキルカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基等が挙げられる。これらの中でも、置換基として、アルキル基、又はアルコキシ基を有することが好ましく、分岐アルキル基又はアルコキシ基を有することがより好ましく、炭素数3~10の分岐アルキル基、又は、炭素数1~10のアルコキシ基を有することが更に好ましい。
R11及びR12は同一の基であっても、異なる基であってもよいが、合成適性上の観点からは、同一の基であることが好ましい。 In formula (104), R 11 and R 12 each independently represent a hydrocarbon group.
R 11 and R 12 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
R 11 and R 12 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have an alkoxy group of.
R 11 and R 12 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
本発明において、ホスホニウム塩とは、ホスホニウムカチオンと、アニオンとの塩を意味する。アニオンとしては、上述のアンモニウム塩におけるアニオンと同様のものが例示され、好ましい態様も同様である。 [Phoenium salt]
In the present invention, the phosphonium salt means a salt of a phosphonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
ホスホニウムカチオンとしては、第四級ホスホニウムカチオンが好ましく、テトラアルキルホスホニウムカチオン、トリアリールモノアルキルホスホニウムカチオン等が挙げられる。
また、ホスホニウムカチオンとしては、下記式(105)で表されるカチオンが好ましい。
As the phosphonium cation, a quaternary phosphonium cation is preferable, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation.
Further, as the phosphonium cation, a cation represented by the following formula (105) is preferable.
R13~R16はそれぞれ独立に、アルキル基又はアリール基であることが好ましく、炭素数1~10のアルキル基又は炭素数6~12のアリール基であることがより好ましく、炭素数6~12のアリール基であることが更に好ましく、フェニル基であることが更に好ましい。
R13~R16は置換基を有していてもよく、置換基の例としては、ヒドロキシ基、アリール基、アルコキシ基、アリールオキシ基、アリールカルボニル基、アルキルカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基等が挙げられる。これらの中でも、置換基として、アルキル基、又はアルコキシ基を有することが好ましく、分岐アルキル基又はアルコキシ基を有することがより好ましく、炭素数3~10の分岐アルキル基、又は、炭素数1~10のアルコキシ基を有することが更に好ましい。
R13~R16は同一の基であっても、異なる基であってもよいが、合成適性上の観点からは、同一の基であることが好ましい。 In formula (105), R 13 to R 16 each independently represent a hydrogen atom or a hydrocarbon group.
R 13 to R 16 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
R 13 to R 16 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have an alkoxy group of.
R 13 to R 16 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
オニウム塩は、1種又は2種以上を用いることができる。2種以上を用いる場合は、合計量が上記範囲であることが好ましい。 When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
As the onium salt, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
本発明の硬化性樹脂組成物は、熱塩基発生剤を更に含んでもよい。
特に、本発明の硬化性樹脂組成物が特定樹脂としてポリイミド前駆体又はポリベンゾオキサゾール前駆体を含む場合、熱塩基発生剤を含むことが好ましい。
他の熱塩基発生剤は、上述のオニウム塩に該当する化合物であってもよいし、上述のオニウム塩以外の熱塩基発生剤であってもよい。
上述のオニウム塩以外の熱塩基発生剤としては、ノニオン系熱塩基発生剤が挙げられる。
ノニオン系熱塩基発生剤としては、式(B1)又は式(B2)で表される化合物が挙げられる。
The curable resin composition of the present invention may further contain a thermosetting agent.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to contain a thermosetting agent.
The other thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
Examples of the thermobase generator other than the above-mentioned onium salt include nonionic thermobase generators.
Examples of the nonionic thermobase generator include compounds represented by the formula (B1) or the formula (B2).
Rb13はアルキル基(炭素数1~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アルケニル基(炭素数2~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)であり、本発明の効果を奏する範囲で置換基を有していてもよい。中でも、Rb13はアリールアルキル基が好ましい。 In the formula, 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. Of these, Rb 13 is preferably an arylalkyl group.
Rb15及びRb16は水素原子、アルキル基(炭素数1~12が好ましく、1~6がより好ましく、1~3が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~6がより好ましく、2~3が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~10が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~11が更に好ましい)であり、水素原子又はメチル基が好ましい。
Rb17はアルキル基(炭素数1~24が好ましく、1~12がより好ましく、3~8が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~10がより好ましく、3~8が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)であり、中でもアリール基が好ましい。 Rb 11 and Rb 12 have the same meanings as 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, further 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, further preferably 6 to 10 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, 7). ~ 19 is more preferable, and 7 to 11 is more preferable), and a hydrogen atom or a methyl group is preferable.
Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), 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), 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.
本発明の硬化性樹脂組成物は、架橋剤を含むことが好ましい。
架橋剤としては、ラジカル架橋剤、又は、他の架橋剤が挙げられる。 <Crosslinking agent>
The curable resin composition of the present invention preferably contains a cross-linking agent.
Examples of the cross-linking agent include radical cross-linking agents and other cross-linking agents.
本発明の硬化性樹脂組成物は、ラジカル架橋剤を更に含むことが好ましい。
ラジカル架橋剤は、ラジカル重合性基を有する化合物である。ラジカル重合性基としては、エチレン性不飽和結合を含む基が好ましい。上記エチレン性不飽和結合を含む基としては、ビニル基、アリル基、ビニルフェニル基、(メタ)アクリロイル基などのエチレン性不飽和結合を有する基が挙げられる。
これらの中でも、上記エチレン性不飽和結合を含む基としては、(メタ)アクリロイル基が好ましく、反応性の観点からは、(メタ)アクリロキシ基がより好ましい。 <Radical cross-linking agent>
The curable resin composition of the present invention preferably further contains a radical cross-linking agent.
The radical cross-linking agent is a compound having a radically polymerizable group. As the 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, and a (meth) acryloyl group.
Among these, the (meth) acryloyl group is preferable as the group containing the ethylenically unsaturated bond, and the (meth) acryloyl group is more preferable from the viewpoint of reactivity.
エチレン性不飽和結合を2個有する化合物は、上記エチレン性不飽和結合を含む基を2個有する化合物であることが好ましい。
また、得られるパターン(硬化膜)の膜強度の観点からは、本発明の硬化性樹脂組成物は、ラジカル架橋剤として、エチレン性不飽和結合を3個以上有する化合物を含むことが好ましい。上記エチレン性不飽和結合を3個以上有する化合物としては、エチレン性不飽和結合を3~15個有する化合物が好ましく、エチレン性不飽和結合を3~10個有する化合物がより好ましく、3~6個有する化合物が更に好ましい。
また、上記エチレン性不飽和結合を3個以上有する化合物は、上記エチレン性不飽和結合を含む基を3個以上有する化合物であることが好ましく、3~15個有する化合物であることがより好ましく、3~10個有する化合物であることが更に好ましく、3~6個有する化合物であることが特に好ましい。
また、得られるパターン(硬化膜)の膜強度の観点からは、本発明の硬化性樹脂組成物は、エチレン性不飽和結合を2個有する化合物と、上記エチレン性不飽和結合を3個以上有する化合物とを含むことも好ましい。 The radical cross-linking agent may be a compound having one or more ethylenically unsaturated bonds, but is more preferably a compound having two or more ethylenically unsaturated bonds.
The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above ethylenically unsaturated bonds.
Further, from the viewpoint of the film strength of the obtained pattern (cured film), the curable resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical cross-linking agent. As the compound having 3 or more ethylenically unsaturated bonds, a compound having 3 to 15 ethylenically unsaturated bonds is preferable, and a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and 3 to 6 compounds are more preferable. The compound having is more preferable.
The compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bond, and more preferably a compound having 3 to 15 ethylenically unsaturated bonds. A compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
Further, from the viewpoint of the film strength of the obtained pattern (cured film), the curable resin composition of the present invention has a compound having two ethylenically unsaturated bonds and three or more ethylenically unsaturated bonds. It is also preferable to include a compound.
また、パターン(硬化膜)の弾性率制御に伴う反り抑制の観点から、ラジカル架橋剤として、単官能ラジカル架橋剤を好ましく用いることができる。単官能ラジカル架橋剤としては、n-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、カルビトール(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、N-メチロール(メタ)アクリルアミド、グリシジル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート等の(メタ)アクリル酸誘導体、N-ビニルピロリドン、N-ビニルカプロラクタム等のN-ビニル化合物類、アリルグリシジルエーテル、ジアリルフタレート、トリアリルトリメリテート等のアリル化合物類等が好ましく用いられる。単官能ラジカル架橋剤としては、露光前の揮発を抑制するため、常圧下で100℃以上の沸点を持つ化合物も好ましい。 For the curable resin composition of the present invention, it is preferable to use bifunctional metal acrylate 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, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, and polytetraethylene. Glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol Dimethacrylate, dimethylol-tricyclodecanediacrylate, dimethylol-tricyclodecanedimethacrylate, EO adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, PO of bisphenol A Additives Dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates having urethane bonds can be used. it can. If necessary, two or more of these can be mixed and used. For example, the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula of about 200.
Further, from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the pattern (cured film), a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent. 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. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used. As 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.
本発明の硬化性樹脂組成物は、上述したラジカル架橋剤とは異なる、他の架橋剤を含むことが好ましい。
本発明において、他の架橋剤とは、上述したラジカル架橋剤以外の架橋剤をいい、上述の感光剤の感光により、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が促進される基を分子内に複数個有する化合物であることが好ましく、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が酸又は塩基の作用によって促進される基を分子内に複数個有する化合物が好ましい。
上記酸又は塩基は、第一領域露光工程、第二領域露光工程等の露光工程において、感光剤である光酸発生剤又は光塩基発生剤から発生する酸又は塩基であることが好ましい。
他の架橋剤としては、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも一種の基を有する化合物が好ましく、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも一種の基が窒素原子に直接結合した構造を有する化合物がより好ましい。
他の架橋剤としては、例えば、メラミン、グリコールウリル、尿素、アルキレン尿素、ベンゾグアナミンなどのアミノ基含有化合物にホルムアルデヒド又はホルムアルデヒドとアルコールを反応させ、上記アミノ基の水素原子をメチロール基又はアルコキシメチル基で置換した構造を有する化合物が挙げられる。これらの化合物の製造方法は特に限定されず、上記方法により製造された化合物と同様の構造を有する化合物であればよい。また、これらの化合物のメチロール基同士が自己縮合してなるオリゴマーであってもよい。
上記のアミノ基含有化合物として、メラミンを用いた架橋剤をメラミン系架橋剤、グリコールウリル、尿素又はアルキレン尿素を用いた架橋剤を尿素系架橋剤、アルキレン尿素を用いた架橋剤をアルキレン尿素系架橋剤、ベンゾグアナミンを用いた架橋剤をベンゾグアナミン系架橋剤という。
これらの中でも、本発明の硬化性樹脂組成物は、尿素系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことが好ましく、後述するグリコールウリル系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことがより好ましい。 <Other cross-linking agents>
The curable resin composition of the present invention preferably contains another cross-linking agent different from the radical cross-linking agent described above.
In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and a covalent bond is formed with another compound in the composition or a reaction product thereof by exposure to the above-mentioned photosensitizer. It is preferable that the compound has a plurality of groups in the molecule for which the reaction to be formed is promoted, and the reaction of forming a covalent bond with another compound in the composition or a reaction product thereof is the action of an acid or a base. A compound having a plurality of groups promoted by the above in the molecule is preferable.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator, which is a photosensitizer, in an exposure step such as a first region exposure step or a second region exposure step.
As the other cross-linking agent, a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is a nitrogen atom. A compound having a structure directly bonded to is more preferable.
As another cross-linking agent, for example, 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 a methylol group or an alkoxymethyl group. Examples thereof include compounds having a substituted structure. The method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
As the above amino group-containing compound, 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, and 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.
Among these, the curable 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 preferably contains a glycoluril-based cross-linking agent and melamine, which will be described later. It is more preferable to contain at least one compound selected from the group consisting of system cross-linking agents.
ビスメトキシメチル尿素、ビスエトキシメチル尿素、ビスプロポキシメチル尿素、ビスブトキシメチル尿素等の尿素系架橋剤、
モノヒドロキシメチル化エチレン尿素又はジヒドロキシメチル化エチレン尿素、モノメトキシメチル化エチレン尿素、ジメトキシメチル化エチレン尿素、モノエトキシメチル化エチレン尿素、ジエトキシメチル化エチレン尿素、モノプロポキシメチル化エチレン尿素、ジプロポキシメチル化エチレン尿素、モノブトキシメチル化エチレン尿素、又は、ジブトキシメチル化エチレン尿素などのエチレン尿素系架橋剤、
モノヒドロキシメチル化プロピレン尿素、ジヒドロキシメチル化プロピレン尿素、モノメトキシメチル化プロピレン尿素、ジメトキシメチル化プロピレン尿素、モノジエトキシメチル化プロピレン尿素、ジエトキシメチル化プロピレン尿素、モノプロポキシメチル化プロピレン尿素、ジプロポキシメチル化プロピレン尿素、モノブトキシメチル化プロピレン尿素、又は、ジブトキシメチル化プロピレン尿素などのプロピレン尿素系架橋剤、
1,3-ジ(メトキシメチル)4,5-ジヒドロキシ-2-イミダゾリジノン、1,3-ジ(メトキシメチル)-4,5-ジメトキシ-2-イミダゾリジノンなどが挙げられる。 Specific examples of the urea-based cross-linking agent include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol uryl. , Trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monomethoxymethylated glycol uryl, dimethoxymethylated glycol uryl, trimethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl, di Propoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol uryl, etc. Glycoluryl-based cross-linking agent;
Urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea,
Monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethyl Ethyleneurea-based cross-linking agents such as ethyleneurea, monobutoxymethylated, or dibutoxymethylated ethyleneurea,
Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxy A propylene urea-based cross-linking agent such as methylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea,
Examples thereof include 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone and 1,3-di (methoxymethyl) -4,5-dimethoxy-2-imidazolidinone.
このような化合物の具体例としては、ベンゼンジメタノール、ビス(ヒドロキシメチル)クレゾール、ビス(ヒドロキシメチル)ジメトキシベンゼン、ビス(ヒドロキシメチル)ジフェニルエーテル、ビス(ヒドロキシメチル)ベンゾフェノン、ヒドロキシメチル安息香酸ヒドロキシメチルフェニル、ビス(ヒドロキシメチル)ビフェニル、ジメチルビス(ヒドロキシメチル)ビフェニル、ビス(メトキシメチル)ベンゼン、ビス(メトキシメチル)クレゾール、ビス(メトキシメチル)ジメトキシベンゼン、ビス(メトキシメチル)ジフェニルエーテル、ビス(メトキシメチル)ベンゾフェノン、メトキシメチル安息香酸メトキシメチルフェニル、ビス(メトキシメチル)ビフェニル、ジメチルビス(メトキシメチル)ビフェニル、4,4’,4’’-エチリデントリス[2,6-ビス(メトキシメチル)フェノール]、5,5’-[2,2,2‐トリフルオロ‐1‐(トリフルオロメチル)エチリデン]ビス[2‐ヒドロキシ‐1,3‐ベンゼンジメタノール]、3,3’,5,5’-テトラキス(メトキシメチル)-1,1’-ビフェニル-4,4’-ジオール等が挙げられる。 In addition, as a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring). A compound to which a group is directly bonded is also preferably used.
Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylbenzoate hydroxymethylphenyl. , Bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) Benzenephenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, 4,4', 4''-ethylidentris [2,6-bis (methoxymethyl) phenol], 5 , 5'-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 3,3', 5,5'-tetrakis ( Methoxymethyl) -1,1'-biphenyl-4,4'-diol and the like can be mentioned.
エポキシ化合物としては、一分子中にエポキシ基を2以上有する化合物であることが好ましい。エポキシ基は、200℃以下で架橋反応し、かつ、架橋に由来する脱水反応が起こらないため膜収縮が起きにくい。このため、エポキシ化合物を含有することは、硬化性樹脂組成物の低温硬化及び反りの抑制に効果的である。 [Epoxy compound (compound having an epoxy group)]
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Since 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, film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the curable resin composition.
オキセタン化合物としては、一分子中にオキセタン環を2つ以上有する化合物、3-エチル-3-ヒドロキシメチルオキセタン、1,4-ビス{[(3-エチル-3-オキセタニル)メトキシ]メチル}ベンゼン、3-エチル-3-(2-エチルヘキシルメチル)オキセタン、1,4-ベンゼンジカルボン酸-ビス[(3-エチル-3-オキセタニル)メチル]エステル等を挙げることができる。具体的な例としては、東亞合成(株)製のアロンオキセタンシリーズ(例えば、OXT-121、OXT-221、OXT-191、OXT-223)が好適に使用することができ、これらは単独で、又は2種以上混合してもよい。 [Oxetane compound (compound having an oxetanyl group)]
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and the like. Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like. As a specific example, the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone. Alternatively, two or more types may be mixed.
ベンゾオキサジン化合物は、開環付加反応に由来する架橋反応のため、硬化時に脱ガスが発生せず、更に熱収縮を小さくして反りの発生が抑えられることから好ましい。 [Benzoxazine compound (compound having a benzoxazolyl group)]
Since the benzoxazine compound is a cross-linking reaction derived from the cycloaddition reaction, degassing does not occur during curing, and the heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.
本発明の硬化性樹脂組成物は、更にマイグレーション抑制剤を含むことが好ましい。マイグレーション抑制剤を含むことにより、金属層(金属配線)由来の金属イオンが硬化性樹脂組成物層内へ移動することを効果的に抑制可能となる。
本発明において、上述のトリアゾール構造を有する化合物は、マイグレーション抑制剤には該当しないものとする。 <Migration inhibitor>
The curable resin composition of the present invention preferably further contains 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 curable resin composition layer.
In the present invention, the above-mentioned compound having a triazole structure does not correspond to a migration inhibitor.
本発明の硬化性樹脂組成物は、重合禁止剤を含むことが好ましい。 <Polymerization inhibitor>
The curable resin composition of the present invention preferably contains a polymerization inhibitor.
本発明の硬化性樹脂組成物は、電極や配線などに用いられる金属材料との接着性を向上させるための金属接着性改良剤を含んでいることが好ましい。金属接着性改良剤としては、シランカップリング剤、アルミニウム系接着助剤、チタン系接着助剤、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物、リン酸誘導体化合物、βケトエステル化合物、アミノ化合物等などが挙げられる。 <Metal adhesion improver>
The curable 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. Examples of the metal adhesion improver include silane coupling agents, aluminum-based adhesive aids, titanium-based adhesive aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds and the like. And so on.
他のシランカップリング剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシラン、p-スチリルトリメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-アクリロキシプロピルトリメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン、N-フェニル-3-アミノプロピルトリメトキシシラン、トリス-(トリメトキシシリルプロピル)イソシアヌレー、3-ウレイドプロピルトリアルコキシシラン、3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-イソシアネートプロピルトリエトキシシラン、3-トリメトキシシリルプロピルコハク酸無水物が挙げられる。これらは1種単独または2種以上を組み合わせて使用することができる。
Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid. Xipropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-Phyl-3-aminopropyltrimethoxysilane, Tris- (trimethoxysilylpropyl) isocyanure, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanuppropyl Examples thereof include triethoxysilane and 3-trimethoxysilylpropyl succinate anhydride. These can be used individually by 1 type or in combination of 2 or more types.
アルミニウム系接着助剤としては、例えば、アルミニウムトリス(エチルアセトアセテート)、アルミニウムトリス(アセチルアセトネート)、エチルアセトアセテートアルミニウムジイソプロピレート等を挙げることができる。 [Aluminum-based adhesive aid]
Examples of the aluminum-based adhesive aid include aluminum tris (ethylacetacetate), aluminumtris (acetylacetoneate), ethylacetacetate aluminum diisopropirate, and the like.
本発明の硬化性樹脂組成物は、本発明の効果が得られる範囲で、必要に応じて、各種の添加物、例えば、増感剤、連鎖移動剤、界面活性剤、高級脂肪酸誘導体、無機粒子、硬化剤、硬化触媒、充填剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を配合することができる。これらの添加剤を配合する場合、その合計配合量は硬化性樹脂組成物の固形分の3質量%以下とすることが好ましい。 <Other additives>
The curable resin composition of the present invention contains various additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, and inorganic particles, if necessary, as long as the effects of the present invention can be obtained. , Curing agent, curing catalyst, filler, antioxidant, ultraviolet absorber, anti-aggregation agent and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.
本発明の硬化性樹脂組成物は、増感剤を含んでいてもよい。増感剤は、特定の活性放射線を吸収して電子励起状態となる。電子励起状態となった増感剤は、熱硬化促進剤、熱ラジカル重合開始剤、光ラジカル重合開始剤などと接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより、熱硬化促進剤、熱ラジカル重合開始剤、光ラジカル重合開始剤は化学変化を起こして分解し、ラジカル、酸又は塩基を生成する。
増感剤としては、増感色素を用いてもよい。
増感色素の詳細については、特開2016-027357号公報の段落0161~0163の記載を参酌でき、この内容は本明細書に組み込まれる。 [Sensitizer]
The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electron-excited state. The sensitizer in the electronically excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases.
As the sensitizer, a sensitizing dye may be used.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.
本発明の硬化性樹脂組成物は、連鎖移動剤を含有してもよい。連鎖移動剤は、例えば高分子辞典第三版(高分子学会編、2005年)683-684頁に定義されている。連鎖移動剤としては、例えば、分子内にSH、PH、SiH、及びGeHを有する化合物群が用いられる。これらは、低活性のラジカルに水素を供与して、ラジカルを生成するか、若しくは、酸化された後、脱プロトンすることによりラジカルを生成しうる。特に、チオール化合物を好ましく用いることができる。 [Chain transfer agent]
The curable 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. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, a thiol compound can be preferably used.
本発明の硬化性樹脂組成物には、塗布性をより向上させる観点から、各種類の界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種類の界面活性剤を使用できる。また、下記界面活性剤も好ましい。下記式中、主鎖の繰返し単位を示す括弧は各繰返し単位の含有量(モル%)を、側鎖の繰返し単位を示す括弧は各繰返し単位の繰り返し数をそれぞれ表す。
また、界面活性剤は、国際公開第2015/199219号の段落0159~0165に記載の化合物を用いることもできる。
フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する含フッ素重合体をフッ素系界面活性剤として用いることもできる。具体例としては、特開2010-164965号公報の段落0050~0090および段落0289~0295に記載された化合物、例えばDIC(株)製のメガファックRS-101、RS-102、RS-718K等が挙げられる。 [Surfactant]
Each type of surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. The following surfactants are also preferable. In the following formula, the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit, and the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.
Further, as the surfactant, the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
As the 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 include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP2010-164965, such as Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. Can be mentioned.
本発明の硬化性樹脂組成物は、酸素に起因する重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体を添加して、塗布後の乾燥の過程で硬化性樹脂組成物の表面に偏在させてもよい。 [Higher fatty acid derivative]
The curable resin composition of the present invention has a curable resin composition in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of an object.
本発明の樹脂組成物は、熱重合開始剤を含んでもよく、特に熱ラジカル重合開始剤を含んでもよい。熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性を有する化合物の重合反応を開始又は促進させる化合物である。熱ラジカル重合開始剤を添加することによって樹脂及び重合性化合物の重合反応を進行させることもできるので、より耐溶剤性を向上できる。 [Thermal polymerization initiator]
The resin composition of the present invention may contain a thermal polymerization initiator, and in particular, a thermal radical polymerization initiator. A 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 allowed to proceed by adding the thermal radical polymerization initiator, the solvent resistance can be further improved.
本発明の樹脂組成物は、無機粒子を含んでもよい。無機粒子として、具体的には、炭酸カルシウム、リン酸カルシウム、シリカ、カオリン、タルク、二酸化チタン、アルミナ、硫酸バリウム、フッ化カルシウム、フッ化リチウム、ゼオライト、硫化モリブデン、ガラス等を含むことができる。 [Inorganic particles]
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.
上記無機粒子の平均粒子径を多量に含有させることによって、上記硬化膜の機械特性が劣化することがある。また、上記無機粒子の平均粒子径が2.0μmを超えると、露光光の散乱によって解像度が低下することがある。 The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Especially preferable.
By containing a large amount of the average particle size of the inorganic particles, the mechanical properties of the cured film may deteriorate. Further, if the average particle size of the inorganic particles exceeds 2.0 μm, the resolution may decrease due to scattering of exposure light.
本発明の組成物は、紫外線吸収剤を含んでいてもよい。紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、トリアジン系などの紫外線吸収剤を使用することができる。
サリシレート系紫外線吸収剤の例としては、フェニルサリシレート、p-オクチルフェニルサリシレート、p-t-ブチルフェニルサリシレートなどが挙げられ、ベンゾフェノン系紫外線吸収剤の例としては、2,2’-ジヒドロキシ-4-メトキシベンゾフェノン、2,2’-ジヒドロキシ-4,4’-ジメトキシベンゾフェノン、2,2’,4,4’-テトラヒドロキシベンゾフェノン、2-ヒドロキシ-4-メトキシベンゾフェノン、2,4-ジヒドロキシベンゾフェノン、2-ヒドロキシ-4-オクトキシベンゾフェノンなどが挙げられる。また、ベンゾトリアゾール系紫外線吸収剤の例としては、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-ブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-アミル-5’-イソブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-プロピルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)ベンゾトリアゾール、2-(2’-ヒドロキシ-5’-メチルフェニル)ベンゾトリアゾール、2-[2’-ヒドロキシ-5’-(1,1,3,3-テトラメチル)フェニル]ベンゾトリアゾールなどが挙げられる。 [UV absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and examples of benzophenone-based ultraviolet 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- Hydroxy-4-octoxybenzophenone and the like can be mentioned. Examples of benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3). '-Tert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2-( 2'-Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5' -(1,1,3,3-tetramethyl) phenyl] benzotriazole and the like can be mentioned.
本発明の組成物は、紫外線吸収剤を含んでも含まなくてもよいが、含む場合、紫外線吸収剤の含有量は、本発明の組成物の全固形分質量に対して、0.001質量%以上1質量%以下であることが好ましく、0.01質量%以上0.1質量%以下であることがより好ましい。 In the present invention, 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.
本実施形態の樹脂組成物は、有機チタン化合物を含有してもよい。樹脂組成物が有機チタン化合物を含有することにより、低温で硬化した場合であっても耐薬品性に優れる樹脂層を形成できる。 [Organic titanium compound]
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.
有機チタン化合物の具体例を、以下のI)~VII)に示す:
I)チタンキレート化合物:中でも、ネガ型感光性樹脂組成物の保存安定性がよく、良好な硬化パターンが得られることから、アルコキシ基を2個以上有するチタンキレート化合物がより好ましい。具体的な例は、チタニウムビス(トリエタノールアミン)ジイソプロポキサイド、チタニウムジ(n-ブトキサイド)ビス(2,4-ペンタンジオネート、チタニウムジイソプロポキサイドビス(2,4-ペンタンジオネート)、チタニウムジイソプロポキサイドビス(テトラメチルヘプタンジオネート)、チタニウムジイソプロポキサイドビス(エチルアセトアセテート)等である。
II)テトラアルコキシチタン化合物:例えば、チタニウムテトラ(n-ブトキサイド)、チタニウムテトラエトキサイド、チタニウムテトラ(2-エチルヘキソキサイド)、チタニウムテトライソブトキサイド、チタニウムテトライソプロポキサイド、チタニウムテトラメトキサイド、チタニウムテトラメトキシプロポキサイド、チタニウムテトラメチルフェノキサイド、チタニウムテトラ(n-ノニロキサイド)、チタニウムテトラ(n-プロポキサイド)、チタニウムテトラステアリロキサイド、チタニウムテトラキス[ビス{2,2-(アリロキシメチル)ブトキサイド}]等である。
III)チタノセン化合物:例えば、ペンタメチルシクロペンタジエニルチタニウムトリメトキサイド、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロフェニル)チタニウム、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)フェニル)チタニウム等である。
IV)モノアルコキシチタン化合物:例えば、チタニウムトリス(ジオクチルホスフェート)イソプロポキサイド、チタニウムトリス(ドデシルベンゼンスルホネート)イソプロポキサイド等である。
V)チタニウムオキサイド化合物:例えば、チタニウムオキサイドビス(ペンタンジオネート)、チタニウムオキサイドビス(テトラメチルヘプタンジオネート)、フタロシアニンチタニウムオキサイド等である。
VI)チタニウムテトラアセチルアセトネート化合物:例えば、チタニウムテトラアセチルアセトネート等である。
VII)チタネートカップリング剤:例えば、イソプロピルトリドデシルベンゼンスルホニルチタネート等である。 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 negative photosensitive resin composition has good storage stability and a good curing pattern can be obtained. Specific examples are titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanionate, titanium diisopropoxyside bis (2,4-pentanionate)). , Titanium diisopropoxyside bis (tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
II) Tetraalkoxytitanium 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 Butokiside}] etc.
III) Titanosen compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compound: For example, titanium tris (dioctyl phosphate) isopropoxyside, titanium tris (dodecylbenzene sulfonate) isopropoxide, and the like.
V) Titanium oxide compound: For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetone compound: For example, titanium tetraacetylacetone.
VII) Titanate Coupling Agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.
本発明の組成物は、酸化防止剤を含んでいてもよい。添加剤として酸化防止剤を含有することで、硬化後の膜の伸度特性や、金属材料との密着性を向上させることができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位(オルト位)に置換基を有する化合物が好ましい。前述の置換基としては炭素数1~22の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス[2-[[2,4,8,10-テトラキス(1,1-ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル]オキシ]エチル]アミン、トリス[2-[(4,6,9,11-テトラ-tert-ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン-2-イル)オキシ]エチル]アミン、亜リン酸エチルビス(2,4-ジ-tert-ブチル-6-メチルフェニル)などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ AO-20、アデカスタブ AO-30、アデカスタブ AO-40、アデカスタブ AO-50、アデカスタブ AO-50F、アデカスタブ AO-60、アデカスタブ AO-60G、アデカスタブ AO-80、アデカスタブ AO-330(以上、(株)ADEKA製)などが挙げられる。また、酸化防止剤は、特許第6268967号公報の段落番号0023~0048に記載された化合物を使用することもできる。また、本発明の組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、100~250℃で加熱するか、又は酸/塩基触媒存在下で80~200℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開第2014/021023号、国際公開第2017/030005号、特開2017-008219号公報に記載された化合物が挙げられる。潜在酸化防止剤の市販品としては、アデカアークルズGPA-5001((株)ADEKA製)等が挙げられる。好ましい酸化防止剤の例としては、2,2-チオビス(4-メチル-6-t-ブチルフェノール)、2,6-ジ-t-ブチルフェノールおよび一般式(3)で表される化合物が挙げられる。 〔Antioxidant〕
The composition of the present invention may contain 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. Examples of the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like. As 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. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As a phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6 -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like. Commercially available products of 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, Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used. In addition, 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. As a result, a compound in which the protecting group is eliminated and functions as an antioxidant can be mentioned. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like. Examples of preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds represented by the general formula (3).
本発明の硬化性樹脂組成物の水分含有量は、塗布面性状の観点から、5質量%未満が好ましく、1質量%未満がより好ましく、0.6質量%未満が更に好ましい。水分の含有量を維持する方法としては、保管条件における湿度の調整、収容容器の空隙率低減などが挙げられる。 <Restrictions on other contained substances>
The water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties. Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container.
ハロゲン原子の含有量を調節する方法としては、イオン交換処理などが好ましく挙げられる。 Considering the use as a semiconductor material, the curable 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 more preferably 200 mass ppm from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. 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. Examples of 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.
As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.
本発明の硬化性樹脂組成物は、再配線層用層間絶縁膜の形成に用いられることが好ましい。
また、その他、半導体デバイスの絶縁膜の形成、又は、ストレスバッファ膜の形成等にも用いることができる。 <Use of curable resin composition>
The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer.
In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.
本発明の硬化性樹脂組成物は、上記各成分を混合して調製することができる。混合方法は特に限定はなく、従来公知の方法で行うことができる。 <Preparation of curable resin composition>
The curable 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.
フィルターを用いたろ過の他、吸着材を用いた不純物の除去処理を行ってもよい。フィルターろ過と吸着材を用いた不純物除去処理とを組み合わせてもよい。吸着材としては、公知の吸着材を用いることができる。例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材が挙げられる。 Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the curable resin composition. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, 5 μm or less is preferable, 3 μm or less is more preferable, and 1 μm or less is further preferable. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. 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. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, 0.01 MPa or more and 1.0 MPa or less is preferable, 0.03 MPa or more and 0.9 MPa or less is more preferable, and 0.05 MPa or more and 0.7 MPa or less is further preferable.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As 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.
次に、硬化膜、積層体、半導体デバイス、及びそれらの製造方法について説明する。 (Cured film, laminate, semiconductor device, and manufacturing method thereof)
Next, a cured film, a laminate, a semiconductor device, and a method for manufacturing them will be described.
本発明の硬化膜の製造方法は、上記膜形成工程、並びに、上記膜を露光する露光工程及び上記膜を現像する現像工程を含むことが好ましい。
また、本発明の硬化膜の製造方法は、上記膜形成工程、及び、必要に応じて上記現像工程を含み、かつ、上記膜を50~450℃で加熱する加熱工程を含むことがより好ましい。
具体的には、以下の(a)~(d)の工程を含むことも好ましい。
(a)硬化性樹脂組成物を基材に適用して膜(硬化性樹脂組成物層)を形成する膜形成工程
(b)膜形成工程の後、膜を露光する露光工程
(c)露光された上記膜を現像する現像工程
(d)現像された上記膜を50~450℃で加熱する加熱工程
上記加熱工程において加熱することにより、露光で硬化した樹脂層を更に硬化させることができる。この加熱工程で、例えば上述の熱塩基発生剤が分解し、十分な硬化性が得られる。 The method for producing a cured film of the present invention (hereinafter, also simply referred to as "the method for producing the present invention") includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film. Is preferable.
The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step for exposing the film, and a developing step for developing the film.
Further, the method for producing a cured film of the present invention more preferably includes the film forming step and, if necessary, the developing step, and also includes a heating step of heating the film at 50 to 450 ° C.
Specifically, it is also preferable to include the following steps (a) to (d).
(A) Film forming step of applying the curable resin composition to a substrate to form a film (curable resin composition layer) (b) Exposure step of exposing the film after the film forming step (c) Exposure Development step for developing the above-mentioned film (d) Heating step for heating the developed above-mentioned film at 50 to 450 ° C. By heating in the above-mentioned heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the above-mentioned thermal base generator is decomposed to obtain sufficient curability.
本発明の好ましい実施形態に係る製造方法は、硬化性樹脂組成物を基材に適用して膜(層状)にする、膜形成工程(層形成工程)を含む。 <Film formation process (layer formation process)>
The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the curable resin composition is applied to a substrate to form a film (layered).
また、これらの基材には表面に密着層や酸化層などの層が設けられていてもよい。本発明では、特に、半導体作製基材が好ましく、シリコン基材、Cu基材およびモールド基材がより好ましい。
また、これらの基材にはヘキサメチルジシラザン(HMDS)等による密着層や酸化層などの層が表面に設けられていてもよい。
また、基材としては、例えば板状の基材(基板)が用いられる。
基材の形状は特に限定されず、円形状であっても矩形状であってもよいが、矩形状であることが好ましい。
基材のサイズとしては、円形状であれば、例えば直径が100~450mmであり、好ましくは200~450mmである。矩形状であれば、例えば短辺の長さが100~1000mmであり、好ましくは200~700mmである。 The type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, There are no particular restrictions on magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like.
Further, these base materials may be provided with a layer such as an adhesion layer or an oxide layer on the surface thereof. In the present invention, 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.
Further, as the base material, for example, a plate-shaped base material (board) is used.
The shape of the base material is not particularly limited, and may be circular or rectangular, but is preferably 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.
また、基材の形状によっても塗布方法を適宜選択でき、ウェハ等の円形基材であればスピンコート法やスプレーコート法、インクジェット法等が好ましく、矩形基材であればスリットコート法やスプレーコート法、インクジェット法等が好ましい。スピンコート法の場合は、例えば、500~2,000rpmの回転数で、10秒~1分程度適用することができる。
また感光性樹脂組成物の粘度や設定する膜厚によっては、300~3,500rpmの回転数で、10~180秒適用することも好ましい。また膜厚の均一性を得るために、複数の回転数を組み合わせて塗布することもできる。
また、あらかじめ仮支持体上に上記付与方法によって付与して形成した塗膜を、基材上に転写する方法を適用することもできる。
転写方法に関しては特開2006-023696号公報の段落0023、0036~0051や、特開2006-047592号公報の段落0096~0108に記載の作製方法を本発明においても好適に用いることができる。
また、基材の端部において余分な膜の除去を行なう工程を行なってもよい。このような工程の例には、エッジビードリンス(EBR)、エアナイフ、バックリンスなどが挙げられる。
また樹脂組成物を基材に塗布する前に基材を種々の溶剤を塗布し、基材の濡れ性を向上させた後に樹脂組成物を塗布するプリウェット工程を採用しても良い。 Specifically, 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. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method.
Further, the coating method can be appropriately selected depending on the shape of the base material. For a circular base material such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular base material, a slit coating method or a spray coating method is preferable. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute.
Further, depending on the viscosity of the photosensitive resin composition and the film thickness to be set, it is preferable to apply the photosensitive resin composition at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. Further, in order to obtain the uniformity of the film thickness, a plurality of rotation speeds can be combined and applied.
Further, it is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate.
Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention.
Further, a step of removing the excess film at the edge of the base material may be performed. Examples of such a process include edge bead rinse (EBR), air knife, back rinse and the like.
Further, a pre-wetting 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.
本発明の製造方法は、上記膜(硬化性樹脂組成物層)を形成後、膜形成工程(層形成工程)の後に、溶剤を除去するために乾燥する工程を含んでいてもよい。好ましい乾燥温度は50~150℃で、70℃~130℃がより好ましく、90℃~110℃が更に好ましい。乾燥時間としては、30秒~20分が例示され、1分~10分が好ましく、3分~7分がより好ましい。 <Drying process>
The production method of the present invention may include a step of forming the film (curable resin composition layer), followed by a film forming step (layer forming step), and then drying to remove the solvent. The preferred drying temperature is 50 to 150 ° C., more preferably 70 ° C. to 130 ° C., still more preferably 90 ° C. to 110 ° C. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
本発明の製造方法は、上記膜(硬化性樹脂組成物層)を露光する露光工程を含んでもよい。露光量は、硬化性樹脂組成物を硬化できる限り特に定めるものではないが、例えば、波長365nmでの露光エネルギー換算で100~10,000mJ/cm2照射することが好ましく、200~8,000mJ/cm2照射することがより好ましい。 <Exposure process>
The production method of the present invention may include an exposure step of exposing the film (curable resin composition layer). The amount of exposure is not particularly determined as long as the curable resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ /. It is more preferable to irradiate with cm 2.
また取り扱いと生産性の観点では、高圧水銀灯のブロード(g,h,i線の3波長)光源や半導体レーザー405nmも好適である。 In relation to the light source, the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples thereof include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, and the like. The curable 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.
From the viewpoint of handling and productivity, a broad (three wavelengths of g, h, and i rays) light source of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.
本発明の製造方法は、露光された膜(硬化性樹脂組成物層)に対して、現像を行う(上記膜を現像する)現像工程を含んでもよい。現像を行うことにより、露光されていない部分(非露光部)が除去される。現像方法は、所望のパターンを形成できれば特に制限は無く、例えばノズルからの現像液の吐出、スプレー噴霧、基材の現像液浸漬などが挙げられ、ノズルからの吐出が好ましく利用される。現像工程には、現像液が連続的に基材に供給され続ける工程、基材上で現像液が略静止状態で保たれる工程、現像液を超音波等で振動させる工程およびそれらを組み合わせた工程などが採用可能である。 <Development process>
The production method of the present invention may include a developing step of developing the exposed film (curable resin composition layer) (developing the film). By developing, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection of a developing solution from a nozzle, spray spraying, immersion of a developing solution in a base material, and the like, and ejection from a nozzle is preferably used. The developing process includes a process in which the developing solution is continuously supplied to the base material, a step in which the developing solution is kept in a substantially stationary state on the base material, a step in which the developing solution is vibrated by ultrasonic waves or the like, and a combination thereof. Processes can be adopted.
現像液としては、有機溶剤を含む現像液、又は、アルカリ水溶液を用いることができる。 Development is carried out using a developing solution. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
As the developing solution, a developing solution containing an organic solvent or an alkaline aqueous solution can be used.
他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。 The developer may further contain other components.
Examples of other components include known surfactants and known defoamers.
現像液の供給方法は、所望のパターンを形成できれば特に制限は無く、基材を現像液に浸漬する方法、基材上にノズルを用いて現像液を供給しパドル現像、または、現像液を連続供給する方法がある。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
現像液の浸透性、非画像部の除去性、製造上の効率の観点から、現像液をストレートノズルで供給する方法、又はスプレーノズルにて連続供給する方法が好ましく、画像部への現像液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。
また、現像液をストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去し、スピン乾燥後に再度ストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去する工程を採用してもよく、この工程を複数回繰り返しても良い。
また現像工程における現像液の供給方法としては、現像液が連続的に基材に供給され続ける工程、基材上で現像液が略静止状態で保たれる工程、基材上で現像液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。 [Method of supplying developer]
The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the developer, the method of supplying the developer on the base material using a nozzle, paddle development, or continuous development. There is a way to supply. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
From the viewpoint of the permeability of the developer, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developer with a straight nozzle or the method of continuously supplying the developer with a spray nozzle is preferable, and the developer is supplied to the image area. 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, and this step may be repeated a plurality of times.
Further, as a method of supplying the developer in the developing process, a step in which the developer is continuously supplied to the base material, a step in which the developer is kept in a substantially stationary state on the base material, and a step in which the developer is superposed on the base material. A process of vibrating with a sound wave or the like and a process of combining them can be adopted.
現像液が有機溶剤を含む現像液である場合、リンス液としては、PGMEA(プロピレングリコールモノエチルエーテルアセテート)、IPA(イソプロパノール)などが挙げられ、好ましくはPGMEAである。また、アルカリ水溶液を含む現像液による現像に対するリンス液としては、水が好ましい。
リンス時間は、10秒~10分間が好ましく、20秒~5分間がより好ましく、5秒~1分が更に好ましい。リンス時のリンス液の温度は、特に定めるものではないが、好ましくは、10~45℃、より好ましくは、18℃~30℃で行うことができる。 After the treatment with the developing solution, further rinsing may be performed. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted. The rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with a solvent contained in the curable resin composition.
When the developer is a developer containing an organic solvent, examples of the rinse solution include PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), and the like, preferably PGMEA. Further, water is preferable as the rinsing solution for development with a developing solution containing an alkaline aqueous solution.
The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, still more preferably 5 seconds to 1 minute. The temperature of the rinsing liquid at the time of rinsing is not particularly specified, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。 The rinse solution may further contain other components.
Examples of other components include known surfactants and known defoamers.
リンス液の供給方法は、所望のパターンを形成できれば特に制限は無く、基材をリンス液に浸漬する方法、基材上でのパドル現像、基材にリンス液をシャワーで供給する方法、基材上にストレートノズル等の手段により現像液を連続供給する方法がある。
リンス液の浸透性、非画像部の除去性、製造上の効率の観点から、リンス液をシャワーノズル、ストレートノズル、スプレーノズルなどで供給する方法があり、スプレーノズルにて連続供給する方法が好ましく、画像部へのリンス液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
すなわち、リンス工程は、リンス液を上記露光後の膜に対してストレートノズルにより供給、又は、連続供給する工程であることが好ましく、リンス液をスプレーノズルにより供給する工程であることがより好ましい。
またリンス工程におけるリンス液の供給方法としては、リンス液が連続的に基材に供給され続ける工程、基材上でリンス液が略静止状態で保たれる工程、基材上でリンス液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。 [Supplying method of rinse liquid]
The method of supplying the rinse liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinse liquid, the paddle development on the base material, the method of supplying the rinse liquid to the base material by a shower, and the base material. There is a method of continuously supplying the developing solution by means such as a straight nozzle on the top.
From the viewpoint of the permeability of the rinse liquid, the removability of non-image areas, and the efficiency of manufacturing, there is a method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously 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 the rinse liquid 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.
That is, 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.
Further, as 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 conditioner or the like and a process of combining them can be adopted.
本発明の製造方法は、現像された上記膜を50~450℃で加熱する工程(加熱工程)を含むことが好ましい。
加熱工程は、膜形成工程(層形成工程)、乾燥工程、及び現像工程の後に含まれることが好ましい。加熱工程では、例えば上述の熱塩基発生剤が分解することにより塩基が発生し、特定樹脂である前駆体の環化反応が進行する。また、本発明の硬化性樹脂組成物は特定樹脂である前駆体以外のラジカル重合性化合物を含んでいてもよいが、未反応の特定樹脂である前駆体以外のラジカル重合性化合物の硬化などもこの工程で進行させることができる。加熱工程における層の加熱温度(最高加熱温度)としては、50℃以上であることが好ましく、80℃以上であることがより好ましく、140℃以上であることが更に好ましく、150℃以上であることが一層好ましく、160℃以上であることがより一層好ましく、170℃以上であることが更に一層好ましい。上限としては、500℃以下であることが好ましく、450℃以下であることがより好ましく、350℃以下であることが更に好ましく、250℃以下であることが一層好ましく、220℃以下であることがより一層好ましい。 <Heating process>
The production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ° C.
The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step. In the heating step, for example, the above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the precursor, which is a specific resin, proceeds. Further, the curable resin composition of the present invention may contain a radically polymerizable compound other than the precursor which is a specific resin, but may also cure a radically polymerizable compound other than the precursor which is an unreacted specific resin. It can be advanced in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable. The upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.
加熱手段としては、特に限定されないが、例えばホットプレート、赤外炉、電熱式オーブン、熱風式オーブンなどが挙げられる。 It is preferable that the heating step is performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
The heating means is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, and a hot air oven.
本発明の製造方法は、現像後の膜(硬化性樹脂組成物層)の表面に金属層を形成する金属層形成工程を含むことが好ましい。 <Metal layer forming process>
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (curable resin composition layer).
本発明の製造方法は、更に、積層工程を含むことが好ましい。 <Laminating process>
The production method of the present invention preferably further includes a laminating step.
また、(d)加熱工程は積層の最後又は中間に一括して行う態様としてもよい。すなわち、(a)~(c)の工程を所定の回数繰り返し行い、その後に(d)の加熱をすることで、積層された硬化性樹脂組成物層を一括で硬化する態様としてもよい。また、(c)現像工程の後には(e)金属層形成工程を含んでもよく、このときにも都度(d)の加熱を行っても、所定回数積層させた後に一括して(d)の加熱を行ってもよい。積層工程には、更に、上記乾燥工程や加熱工程等を適宜含んでいてもよいことは言うまでもない。 The laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step are performed again on the surface of the cured film (resin layer) or the metal layer. , A series of steps including performing in this order. However, the mode may be such that only the film forming step (a) is repeated.
Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated curable resin composition layers all at once. Further, the (c) developing step may be followed by the (e) metal layer forming step, and even if the heating is performed each time (d), the (d) is collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step, and the like as appropriate.
また、積層工程における各層は、組成、形状、膜厚等が同一の層であってもよいし、異なる層であってもよい。 The laminating step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times.
Further, each layer in the laminating step may be a layer having the same composition, shape, film thickness, etc., or may be a different layer.
本発明の積層体の製造方法は、上記金属層および感光性樹脂組成物層の少なくとも一部を表面活性化処理する、表面活性化処理工程を含んでもよい。
表面活性化処理工程は、通常、金属層形成工程の後に行うが、上記露光現像工程の後、感光性樹脂組成物層に表面活性化処理工程を行ってから、金属層形成工程を行ってもよい。
表面活性化処理は、金属層の少なくとも一部のみに行ってもよいし、露光後の感光性樹脂組成物層の少なくとも一部のみに行ってもよいし、金属層および露光後の感光性樹脂組成物層の両方について、それぞれ、少なくとも一部に行ってもよい。表面活性化処理は、金属層の少なくとも一部について行うことが好ましく、金属層のうち、表面に感光性樹脂組成物層を形成する領域の一部または全部に表面活性化処理を行うことが好ましい。このように、金属層の表面に表面活性化処理を行うことにより、その表面に設けられる樹脂層との密着性を向上させることができる。
また、表面活性化処理は、露光後の感光性樹脂組成物層(樹脂層)の一部または全部についても行うことが好ましい。このように、感光性樹脂組成物層の表面に表面活性化処理を行うことにより、表面活性化処理した表面に設けられる金属層や樹脂層との密着性を向上させることができる。
表面活性化処理としては、具体的には、各種原料ガス(酸素、水素、アルゴン、窒素、窒素/水素混合ガス、アルゴン/酸素混合ガスなど)のプラズマ処理、コロナ放電処理、CF4/O2、NF3/O2、SF6、NF3、NF3/O2によるエッチング処理、紫外線(UV)オゾン法による表面処理、塩酸水溶液に浸漬して酸化皮膜を除去した後にアミノ基とチオール基を少なくとも一種有する化合物を含む有機表面処理剤への浸漬処理、ブラシを用いた機械的な粗面化処理から選択され、プラズマ処理が好ましく、特に原料ガスに酸素を用いた酸素プラズマ処理が好ましい。コロナ放電処理の場合、エネルギーは、500~200,000J/m2が好ましく、1000~100,000J/m2がより好ましく、10,000~50,000J/m2が最も好ましい。 (Surface activation treatment process)
The method for producing a laminate of the present invention may include a surface activation treatment step of surface activating at least a part of the metal layer and the photosensitive resin composition layer.
The surface activating treatment step is usually performed after the metal layer forming step, but it is also possible to perform the surface activating treatment step on the photosensitive resin composition layer after the exposure development step and then perform the metal layer forming step. Good.
The surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the photosensitive resin composition layer after exposure, or on the metal layer and the photosensitive resin after exposure. For both of the composition layers, each may be at least partially. 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 in which the photosensitive resin composition layer is formed on the surface. .. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin layer provided on the surface can be improved.
Further, it is preferable that the surface activation treatment is performed on a part or all of the photosensitive resin composition layer (resin layer) after exposure. By performing the surface activating treatment on the surface of the photosensitive resin composition layer in this way, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activating treatment.
Specifically, the surface activation treatment includes plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, CF 4 / O 2 , NF 3 / O 2 , SF 6 , NF 3 , NF 3 / O 2 , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, then amino group and thiol group It is selected from a dipping treatment in an organic surface treatment agent containing at least one compound and a mechanical roughening treatment using a brush, and a plasma treatment is preferable, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferable. For corona discharge treatment, the energy is preferably 500 ~ 200,000J / m 2, more preferably 1000 ~ 100,000J / m 2, and most preferably 10,000 ~ 50,000J / m 2.
4,4’-オキシジフタル酸二無水物(ODPA)155.1gを2リットル容量のセパラブルフラスコに入れ、2-ヒドロキシエチルメタクリレート(HEMA)131.2gとγ-ブチロラクトン400mlを入れて室温下で撹拌し、撹拌しながらピリジン81.5gを加えて反応混合物を得た。反応による発熱の終了後に室温まで放冷し、16時間放置した。
次に、氷冷下において、ジシクロヘキシルカルボジイミド(DCC)206.3gをγ-ブチロラクトン180mlに溶解した溶液を撹拌しながら40分かけて反応混合物に加え、続いて4,4’-ジアミノジフェニルエーテル(DADPE)93.0gをγ-ブチロラクトン350mlに懸濁したものを撹拌しながら60分かけて加えた。更に室温で2時間撹拌した後、エチルアルコール30mlを加えて1時間撹拌し、次に、γ-ブチロラクトン400mlを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。
得られた反応液を3リットルのエチルアルコールに加えて粗ポリマーからなる沈殿物を生成した。生成した粗ポリマーを濾別し、テトラヒドロフラン1.5リットルに溶解して粗ポリマー溶液を得た。得られた粗ポリマー溶液を28リットルの水に滴下してポリマーを沈殿させ、得られた沈殿物を濾別した後、真空乾燥して粉末状のポリマーA-1を得た。ポリマーA-1の分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は20,000であった。 <Synthesis Example 1: Synthesis of Polymer A-1>
Place 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in a 2 liter volume separable flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone, and stir at room temperature. Then, 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After the heat generated by the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.
Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether (DADPE). A suspension of 93.0 g in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and the mixture was stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer A-1. When the molecular weight of the polymer A-1 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.
上記合成例1における4,4’-オキシジフタル酸二無水物155.1gに代えて、3,3’4,4’-ビフェニルテトラカルボン酸二無水物147.1gを用いた以外は、合成例1に記載の方法と同様にして反応を行い、ポリマーB-1を得た。ポリマーB-1の分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は22,000であった。 <Synthesis Example 2: Synthesis of Polymer B-1>
Synthesis Example 1 except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride in Synthesis Example 1. The reaction was carried out in the same manner as described in 1. Polymer B-1 was obtained. When the molecular weight of the polymer B-1 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.
20.0g(64.5ミリモル)の4,4’-オキシジフタル酸二無水物(140°Cで12時間乾燥)と、17.12g(131.58ミリモル)の2-ヒドロキシエチルメタクリレート(HEMA)とを、50mlのN-メチルピロリドンに懸濁させ、モレキュラーシーブで乾燥させた。懸濁液を100℃で3時間加熱した。加熱開始してから数分後に透明な溶液が得られた。反応混合物を室温に冷却し、21.43g(270.9ミリモル)のピリジンおよび90mlのN-メチルピロリドンを加えた。次いで、反応混合物を-10℃に冷却し、温度を-10±4℃に保ちながら16.12g(135.5ミリモル)のSOCl2を10分かけて加えた。SOCl2を加えている間、粘度が増加した。50mlのN-メチルピロリドンで希釈した後、反応混合物を室温で2時間撹拌した。次いで、100mlのN-メチルピロリドンに11.75g(58.7ミリモル)の4,4’-ジアミノジフェニルエーテルを溶解させた溶液を、20~23℃で20分かけて反応混合物に滴下した。次いで、反応混合物を室温で1晩撹拌した。次いで、5リットルの水の中でポリイミド前駆体を沈殿させ、水-ポリイミド前駆体混合物を5000rpmの速度で15分間撹拌した。ポリイミド前駆体を濾取し、再度4リットルの水に投入してさらに30分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体を減圧下で、45℃で3日間乾燥し、ポリマーA-2を得た。 <Synthesis Example 3: Synthesis of Polymer A-2>
With 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (dried at 140 ° C for 12 hours) and 17.12 g (131.58 mmol) of 2-hydroxyethyl methacrylate (HEMA). Was suspended in 50 ml of N-methylpyrrolidone and dried on a molecular sieve. The suspension was heated at 100 ° C. for 3 hours. A clear solution was obtained a few minutes after the start of heating. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 ml of N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCL 2 was added over 10 minutes while keeping the temperature at −10 ± 4 ° C. Viscosity increased while SOCL 2 was added. After diluting with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution prepared by dissolving 11.75 g (58.7 mmol) of 4,4′-diaminodiphenyl ether in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred at room temperature overnight. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, put into 4 liters of water again, stirred for another 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at 45 ° C. for 3 days to obtain polymer A-2.
合成例3において、20.0g(64.5ミリモル)の4,4’-オキシジフタル酸二無水物に代えて、19.0g(64.5ミリモル)の3,3’4,4’-ビフェニルテトラカルボン酸二無水物を用いた以外は、合成例3に記載の方法と同様にして反応を行い、ポリマーB-2を得た。 <Synthesis Example 4: Synthesis of Polymer B-2>
In Synthesis Example 3, 19.0 g (64.5 mmol) of 3,3'4,4'-biphenyltetra instead of 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride The reaction was carried out in the same manner as described in Synthesis Example 3 except that the carboxylic dianhydride was used to obtain polymer B-2.
乾燥窒素気流下、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン(32.78g(0.0895モル))と、1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン(1.24g(0.005モル))とを、NMP 100gに溶解させた。この溶液に、ビス(3,4-ジカルボキシフェニル)エーテル二無水物(31.02g(0.10モル))をNMP 30gとともに加えて、20℃で1時間撹拌し、次いで50℃で4時間撹拌した。この撹拌後の溶液に、3-アミノフェノール(1.09g(0.01モル))を加え、50℃で2時間撹拌した後、180℃で5時間撹拌して樹脂溶液を得た。次に、この樹脂溶液を水(3L)に投入して、白色沈殿を生成させた。この白色沈殿を、濾過で集めて水で3回洗浄した後、80℃の真空乾燥機で5時間乾燥した。この結果、ポリイミドであるポリマーCの粉末が得られた。 <Synthesis Example 5: Synthesis of Polymer C>
2,2-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (32.78 g (0.0895 mol)) and 1,3-bis (3-aminopropyl) tetramethyldi under a dry nitrogen stream. Siloxane (1.24 g (0.005 mol)) was dissolved in 100 g of NMP. To this solution, bis (3,4-dicarboxyphenyl) ether dianhydride (31.02 g (0.10 mol)) was added with 30 g of NMP and stirred at 20 ° C. for 1 hour, then at 50 ° C. for 4 hours. Stirred. 3-Aminophenol (1.09 g (0.01 mol)) was added to the stirred solution, and the mixture was stirred at 50 ° C. for 2 hours and then at 180 ° C. for 5 hours to obtain a resin solution. Next, this resin solution was poured into water (3 L) to generate a white precipitate. The white precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 5 hours. As a result, a powder of polymer C, which is a polyimide, was obtained.
セパラブルフラスコ中で、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)-ヘキサフルオロプロパン 183.1g(0.5モル)、N,N-ジメチルアセトアミド(DMAc) 640.9g、ピリジン 63.3g(0.8モル)を室温(25℃)で混合撹拌し、均一溶液とした。これに、4,4’-ジフェニルエーテルジカルボニルクロリド 118.0g(0.4モル)をジエチレングリコールジメチルエーテル(DMDG) 354gに溶解したものを滴下ロートより滴下した。この際、セパラブルフラスコは15~20℃の水浴で冷却した。滴下に要した時間は40分、反応液温は最大で30℃であった。
滴下終了から3時間後、反応液に1,2-シクロヘキシルジカルボン酸無水物 30.8g(0.2mol)を添加し、室温で15時間撹拌放置し、ポリマー鎖の全アミン末端基の99%をカルボキシシクロヘキシルアミド基で封止した。この際の反応率は投入した1,2-シクロヘキシルジカルボン酸無水物の残量を高速液体クロマトグラフィー(HPLC)で追跡することにより容易に算出することができる。その後上記反応液を2Lの水に高速撹拌下で滴下し重合体を分散析出させ、これを回収し、適宜水洗、脱水の後に真空乾燥を施し、ゲルパーミエーションクロマトグラフィー(GPC)法で測定した重量平均分子量9,000(ポリスチレン換算)の粗ポリベンゾオキサゾール前駆体を得た。
上記で得られた粗ポリベンゾオキサゾール前駆体をγ-ブチロラクトン(GBL)に再溶解した後、これを陽イオン交換樹脂及び陰イオン交換樹脂にて処理し、それにより得られた溶液をイオン交換水中に投入後、析出したポリマーを濾別、水洗、真空乾燥することにより精製されたポリベンゾオキサゾール前駆体(ポリマーD)を得た。 <Synthesis Example 6: Synthesis of Polymer D>
In a separable flask, 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane 183.1 g (0.5 mol), N, N-dimethylacetamide (DMAc) 640.9 g, pyridine 63 .3 g (0.8 mol) was mixed and stirred at room temperature (25 ° C.) to prepare a uniform solution. To this, 118.0 g (0.4 mol) of 4,4'-diphenyl ether dicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 ° C. The time required for dropping was 40 minutes, and the reaction liquid temperature was 30 ° C. at the maximum.
After 3 hours from the completion of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction solution, and the mixture was left to stir for 15 hours at room temperature to remove 99% of all amine terminal groups of the polymer chain. It was sealed with a carboxycyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of the charged 1,2-cyclohexyldicarboxylic acid anhydride by high performance liquid chromatography (HPLC). After that, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water as appropriate, dehydrated, vacuum dried, and measured by a gel permeation chromatography (GPC) method. A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (polystyrene equivalent) was obtained.
The crude polybenzoxazole precursor obtained above is redissolved in γ-butyrolactone (GBL), treated with a cation exchange resin and an anion exchange resin, and the resulting solution is prepared in ion exchange water. The precipitated polymer was filtered, washed with water, and vacuum-dried to obtain a purified polybenzoxazole precursor (polymer D).
300gのPPA(ポリリン酸)に2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン(6F-BAPh)50.0g(0.137モル)と2,2-ビス(4-カルボキシフェニル)ヘキサフルオロプロパン(BIS-B-AF)53.5g(0.137モル)とを加え、窒素気流下で100℃に加熱した後に、約10℃/分の昇温速度で200℃まで加熱して、150分間200℃を維持し、ポリベンゾオキサゾールであるポリマーEを得た。 <Synthesis Example 7: Synthesis of Polymer E>
2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6F-BAPH) 50.0 g (0.137 mol) and 2,2-bis (4-carboxy) in 300 g of PPA (polyphosphoric acid) Phenyl) Hexafluoropropane (BIS-B-AF) 53.5 g (0.137 mol) is added and heated to 100 ° C. under a nitrogen stream, and then heated to 200 ° C. at a heating rate of about 10 ° C./min. Then, the temperature was maintained at 200 ° C. for 150 minutes to obtain polymer E which is a polybenzoxazole.
三口フラスコにN-メチルピロリドン123ml、及び、6FDA(東京化成工業株式会社製、製品番号:H0771)54.97g(0.124mol)を加えて40℃で溶解させ、窒素気流下で撹拌しているところに、2,3,5,6-テトラメチルフェニレンジアミンTeMPD(東京化成工業株式会社製、製品番号:T1457)8.13g(0.049mol)、m-フェニレンジアミン(富士フイルム和光純薬(株)製、製品番号:164-01515)6.69g(0.062mol)、3,5-ジアミノ安息香酸DABA(東京化成工業株式会社製、製品番号:D0294)1.971g(0.012mol)のN-メチルピロリドン84.0ml溶液を30分かけて系内を40℃に保ちつつ滴下した。反応液を40℃で2.5時間撹拌した後、ピリジン(和光純薬株式会社製、製品番号:166-22575)2.94g(0.037mol)、無水酢酸(和光純薬株式会社製、製品番号:018-00286)31.58g(0.31mol)をそれぞれ加えて、さらに80℃で3時間撹拌した。その後、反応液にアセトン676.6mLを加え、希釈した。ステンレス容器にメタノール1.15L、アセトン230mLを加えて撹拌しているところに、反応液のアセトン希釈液を滴下した。得られたポリマー結晶を吸引ろ過し、60℃で送風乾燥させて60.1gのポリマーFを得た。 <Synthesis Example 8: Synthesis of Polymer F>
123 ml of N-methylpyrrolidone and 54.97 g (0.124 mol) of 6FDA (manufactured by Tokyo Chemical Industry Co., Ltd., product number: H0771) are added to a three-necked flask and dissolved at 40 ° C., and the mixture is stirred under a nitrogen stream. By the way, 2,3,5,6-tetramethylphenylenediamine TeMPD (manufactured by Tokyo Chemical Industry Co., Ltd., product number: T1457) 8.13 g (0.049 mol), m-phenylenediamine (Fujifilm Wako Pure Chemical Industries, Ltd.) ), Product number: 164-01515) 6.69 g (0.062 mol), 3,5-diaminobenzoic acid DABA (manufactured by Tokyo Chemical Industry Co., Ltd., product number: D0294) 1.971 g (0.012 mol) N A 84.0 ml solution of -methylpyrrolidone was added dropwise over 30 minutes while maintaining the temperature in the system at 40 ° C. After stirring the reaction solution at 40 ° C. for 2.5 hours, 2.94 g (0.037 mol) of pyridine (manufactured by Wako Pure Chemical Industries, Ltd., product number: 166-22575), acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., product) No .: 018-00286) 31.58 g (0.31 mol) was added, and the mixture was further stirred at 80 ° C. for 3 hours. Then, 676.6 mL of acetone was added to the reaction solution to dilute it. 1.15 L of methanol and 230 mL of acetone were added to a stainless steel container and stirred, and a diluted acetone solution of the reaction solution was added dropwise. The obtained polymer crystals were suction-filtered and air-dried at 60 ° C. to obtain 60.1 g of polymer F.
各実施例又は比較例において、それぞれ、下記表2~表8に記載の成分のうち、塩基性化合物以外の成分を混合し、硬化性樹脂組成物又は比較用組成物を得た。
表2~表8に記載の溶剤以外の各成分の欄における数値は、各成分の含有量(質量部)を表す。
また、溶剤の欄における数値は、使用した溶剤の含有量(質量部)を表す。
得られた硬化性樹脂組成物及び比較用組成物を、細孔の幅が0.8μmのポリテトラフルオロエチレン製フィルターを通して加圧ろ過した。
また、表2~表8中、「-」の記載は該当する成分を組成物が含有していないことを示している。 <Examples and Comparative Examples>
In each Example or Comparative Example, among the components shown in Tables 2 to 8 below, components other than the basic compound were mixed to obtain a curable resin composition or a comparative composition.
The numerical values in the columns of each component other than the solvent shown in Tables 2 to 8 represent the content (parts by mass) of each component.
The numerical value in the solvent column represents the content (parts by mass) of the solvent used.
The obtained curable resin composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm.
Further, in Tables 2 to 8, the description of "-" indicates that the composition does not contain the corresponding component.
・A-1、B-1、A-2、B-2、C~F:上述の合成例で合成したポリマーA-1、ポリマーB-1、ポリマーA-2、ポリマーB-2、ポリマーC~F 〔resin〕
-A-1, B-1, A-2, B-2, C to F: Polymer A-1, polymer B-1, polymer A-2, polymer B-2, polymer C synthesized in the above synthesis example. ~ F
・G-1:1H-ベンゾトリアゾール(DMSO中のpKa=11.9)
・G-2:5-メチル-1H-ベンゾトリアゾール(DMSO中のpKa=11.9)
・G-3:4-メチル-1H-ベンゾトリアゾール(DMSO中のpKa=11.9)
・G-4:トリルトリアゾール(5-メチルー1H-ベンゾトリアゾールと4-メチル-1H-ベンゾトリアゾールとの異性体混合物、DMSO中のpKa=11.9)
・G-5:1,2,3-トリアゾール(DMSO中のpKa=13.9)
・G-6:1,2,4-トリアゾール(DMSO中のpKa=14.8)
・G-7:ベンズイミダゾール(DMSO中のpKa=16.4)
・G-8:インドール(DMSO中のpKa=21.0)
・G-9:1H-テトラゾール(DMSO中のpKa=8.2)
G-7、G-8及びG-9はトリアゾール構造を有しない化合物である。 [Specific compound (compound having a triazole structure)]
G-1: 1H-benzotriazole (pKa = 11.9 in DMSO)
G-2: 5-methyl-1H-benzotriazole (pKa = 11.9 in DMSO)
G-3: 4-methyl-1H-benzotriazole (pKa = 11.9 in DMSO)
G-4: Triltriazole (isomer mixture of 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole, pKa = 11.9 in DMSO)
G-5: 1,2,3-triazole (pKa = 13.9 in DMSO)
G-6: 1,2,4-triazole (pKa = 14.8 in DMSO)
G-7: benzimidazole (pKa in DMSO = 16.4)
G-8: Indole (pKa in DMSO = 21.0)
G-9: 1H-tetrazole (pKa in DMSO = 8.2)
G-7, G-8 and G-9 are compounds having no triazole structure.
・H-1:p-ベンゾキノン
・H-2:4-メトキシフェノール
・H-3:2-ニトロソ-1-ナフト-ル [Polymerization inhibitor]
・ H-1: p-benzoquinone ・ H-2: 4-methoxyphenol ・ H-3: 2-nitroso-1-naphthol
・I-1:1-フェニル-1,2-プロパンジオン-2-(O-エトキシカルボニル)-オキシム
・I-2:NCI 831 (ADEKA社製)
・I-3:Irgacure OXE01 (BASF社製)
・I-4:Irgacure OXE02 (BASF社製)
・I-5:Irgacure 784 (BASF社製)
・I-6:Irgacure 379 (BASF社製)
・I-7:7-ジエチルアミノ-3-エトキシカルボニルクマリン
・I-8:ジアゾナフトキノン
・I-9:Wako WPAG-145(富士フイルム和光純薬(株)製) [Photosensitizer or sensitizer]
-I-1: 1-Phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime-I-2: NCI 831 (manufactured by ADEKA)
-I-3: Irgacure OXE01 (manufactured by BASF)
-I-4: Irgacure OXE02 (manufactured by BASF)
・ I-5: Irgacure 784 (manufactured by BASF)
-I-6: Irgacure 379 (manufactured by BASF)
・ I-7: 7-diethylamino-3-ethoxycarbonylcoumarin ・ I-8: diazonaphthoquinone ・ I-9: Wako WPAG-145 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・J-1:テトラエチレングリコールジメタクリレート
・J-2:ライトエステルBP-6EM(共栄社化学(株)製)
・J-3:ダイセル セロキサイド CEL2081((株)ダイセル製)
・J-4:ヘキサメトキシメチルメラミン [Crosslinking agent]
・ J-1: Tetraethylene glycol dimethacrylate ・ J-2: Light ester BP-6EM (manufactured by Kyoeisha Chemical Co., Ltd.)
・ J-3: Daicel Celoxide CEL2081 (manufactured by Daicel Co., Ltd.)
・ J-4: Hexamethoxymethylmelamine
・K-1:N-[3-(トリエトキシシリル)プロピル]フタルアミド酸
・K-2:N-[3-(トリエトキシシリル)プロピル]マレアミド酸
・K-3:3-メタクリロキシプロピルトリメトキシシラン
・K-4:2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン
・K-5:下記式(K-5)で表される構造の化合物。式(K-5)中、Rはエチル基を表す。
・ K-1: N- [3- (triethoxysilyl) propyl] phthalamic acid ・ K-2: N- [3- (triethoxysilyl) propyl] maleamic acid ・ K-3: 3-methacryloxypropyltrimethoxy Silane K-4: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane K-5: A compound having a structure represented by the following formula (K-5). In formula (K-5), R represents an ethyl group.
・L-1:下記式(L-1)で表される化合物
L-1: A compound represented by the following formula (L-1)
・M-1:N-フェニルジエタノールアミン
・M-2:CyDTA(トランス-1,2シクロヘキサンジアミン四酢酸) [PH regulator]
-M-1: N-Phenyldiethanolamine-M-2: CyDTA (trans-1,2 cyclohexanediaminetetraacetic acid)
・N-1~N-3:下記式(N-1)~式(N-3)で表される構造の化合物。
N-1 to N-3: Compounds having a structure represented by the following formulas (N-1) to (N-3).
・S-1:N-メチルピロリドン
・S-2:乳酸エチル
・S-3:γ-ブチロラクトン
・S-4:ジメチルスルホキシド
・S-5:シクロペンタノン 〔solvent〕
-S-1: N-methylpyrrolidone-S-2: Ethyl lactate-S-3: γ-Butyrolactone-S-4: Dimethyl sulfoxide-S-5: Cyclopentanone
〔腐食抑制(高温高湿保持後の銅-樹脂界面のボイド)評価〕
各実施例及び比較例において、それぞれ、各硬化性樹脂組成物又は各比較用組成物を、銅基板上にスピンコート法により層状に適用(塗布)して、硬化性樹脂組成物層を形成した。
各実施例及び比較例において、得られた組成物層を適用した銅基板をホットプレート上で、100℃で4分間乾燥し、銅基板上に厚さ20μmの硬化性樹脂組成物層を形成した。
表2~表8中、「腐食抑制」の「露光条件」の欄に「i」と記載された例においては、m銅基板上の硬化性樹脂組成物層を、i線(波長約365nm)により、400mJ/cm2の露光エネルギーで100μm四方の正方形状の非マスク部を有するフォトマスクを使用して露光し、さらに、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、3時間の間230℃を維持し、硬化膜が形成された銅基板を得た。
表2~表8中、「腐食抑制」の「露光条件」の欄に「h」と記載された例においては、m銅基板上の硬化性樹脂組成物層を、h線(波長約405nm)により、400mJ/cm2の露光エネルギーで100μm四方の正方形状の非マスク部を有するフォトマスクを使用して露光し、さらに、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、3時間の間230℃を維持し、硬化膜が形成された銅基板を得た。
表2~表8中、「腐食抑制」の「露光条件」の欄に「b」と記載された例においては、m銅基板上の硬化性樹脂組成物層を、ブロードバンド光(高圧水銀灯)により、400mJ/cm2の露光エネルギーで100μm四方の正方形状の非マスク部を有するフォトマスクを使用して露光し、さらに、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、3時間の間230℃を維持し、硬化膜が形成された銅基板を得た。
表2~表8中、「腐食抑制」の「露光条件」の欄に「-」と記載された例においては、銅基板上の硬化性樹脂組成物層を露光せずに窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、3時間の間230℃を維持し、硬化膜が形成された銅基板を得た。 <Evaluation>
[Corrosion suppression (void of copper-resin interface after high temperature and high humidity retention) evaluation]
In each Example and Comparative Example, each curable resin composition or each comparative composition was applied (coated) in layers on a copper substrate by a spin coating method to form a curable resin composition layer. ..
In each Example and Comparative Example, the copper substrate to which the obtained composition layer was applied was dried on a hot plate at 100 ° C. for 4 minutes to form a curable resin composition layer having a thickness of 20 μm on the copper substrate. ..
In the example in which "i" is described in the "exposure condition" column of "corrosion suppression" in Tables 2 to 8, the curable resin composition layer on the m-copper substrate is formed by i-line (wavelength of about 365 nm). With an exposure energy of 400 mJ / cm 2 , exposure was performed using a photomask having a 100 μm square non-masked portion, and further, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere. After reaching 230 ° C., the temperature was maintained at 230 ° C. for 3 hours to obtain a copper substrate on which a cured film was formed.
In the example in which "h" is described in the "exposure condition" column of "corrosion suppression" in Tables 2 to 8, the curable resin composition layer on the m-copper substrate is formed by h-line (wavelength of about 405 nm). With an exposure energy of 400 mJ / cm 2 , exposure was performed using a photomask having a 100 μm square non-masked portion, and further, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere. After reaching 230 ° C., the temperature was maintained at 230 ° C. for 3 hours to obtain a copper substrate on which a cured film was formed.
In the example in which "b" is described in the "exposure condition" column of "corrosion suppression" in Tables 2 to 8, the curable resin composition layer on the m copper substrate is subjected to broadband light (high pressure mercury lamp). , 400 mJ / cm 2 exposure energy using a photomask having a 100 μm square non-masked portion, and further, under a nitrogen atmosphere, the temperature was raised at a heating rate of 10 ° C./min to 230. After reaching the temperature, the temperature was maintained at 230 ° C. for 3 hours to obtain a copper substrate on which a cured film was formed.
In Tables 2 to 8, in the example in which "-" is described in the "Exposure condition" column of "Corrosion suppression", the curable resin composition layer on the copper substrate is not exposed and is placed in a nitrogen atmosphere. The temperature was raised at a heating rate of 10 ° C./min, and after reaching 230 ° C., the temperature was maintained at 230 ° C. for 3 hours to obtain a copper substrate on which a cured film was formed.
続いて、基板における銅層(銅基板)と硬化膜との積層体部分を割断し、さらに上記断面をイオンミリング装置(ArBlade5000、日立ハイテクノロジーズ社製)にて表面処理を行った。
得られた銅層(Cu層)と硬化膜との積層体断面を、FE-SEM(S-4800型、日立ハイテクノロジーズ社製)によって真横から観察し、Cu層の表面に占めるボイドの面積比率を算出した。すなわち、SEM像のボイドである部分とCu層の部分とに目視にて分離した。ボイドの部分の面積を、Cu層全体の面積で割ることで、ボイドの面積比率を算出した。
上記面積比率から、下記評価基準に従って評価を行い、評価結果を表2~表8の「腐食抑制」の欄に記載した。上記ボイドの面積比率が小さいほど、金属の腐食が抑制されているといえる。 The copper substrate on which the cured film was formed was heated in a constant temperature bath (ESPEC STH-120) for 500 hours in air at 150 ° C. and 90% relative humidity.
Subsequently, the laminated body portion of the copper layer (copper substrate) and the cured film on the substrate was cut, and the cross section was further surface-treated with an ion milling apparatus (ArBlade5000, manufactured by Hitachi High-Technologies Corporation).
The cross section of the laminated body of the obtained copper layer (Cu layer) and the cured film was observed from the side by FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Corporation), and the area ratio of voids to the surface of the Cu layer was observed. Was calculated. That is, the void portion of the SEM image and the Cu layer portion were visually separated. The area ratio of the voids was calculated by dividing the area of the void portion by the area of the entire Cu layer.
From the above area ratio, evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the column of "corrosion suppression" in Tables 2 to 8. It can be said that the smaller the area ratio of the voids, the more the metal corrosion is suppressed.
A:上記面積比率が5%以下であった。
B:上記面積比率が5%を超え、15%以下であった。
C:上記面積比率が15%を超えた。 -Evaluation criteria-
A: The area ratio was 5% or less.
B: The area ratio was more than 5% and less than 15%.
C: The area ratio exceeded 15%.
-経時前膜厚の測定-
各実施例及び比較例において、それぞれ、硬化性樹脂組成物又は比較用組成物をスピンコート法でシリコンウェハ上に適用して硬化性樹脂組成物層を形成した。得られた硬化性樹脂組成物層を適用したシリコンウェハをホットプレート上で、100℃で5分間乾燥し、シリコンウェハ上に約15μmの均一な厚さの硬化性樹脂組成物層を得た。上記シリコンウェハ上の硬化性樹脂組成物層の膜厚を測定し、この値を経時前膜厚とした。膜厚は、エリプソメーター(Foothill社製KT-22)で塗布面10点において膜厚測定を実施し、その算術平均値として求めた。 [Evaluation of liquid storage stability]
-Measurement of pre-aging film thickness-
In each Example and Comparative Example, a curable resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a curable resin composition layer. The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a curable resin composition layer having a uniform thickness of about 15 μm on the silicon wafer. The film thickness of the curable resin composition layer on the silicon wafer was measured, and this value was taken as the pre-aging film thickness. The film thickness was determined as an arithmetic mean value obtained by measuring the film thickness at 10 points on the coated surface with an ellipsometer (KT-22 manufactured by Foothill).
各実施例及び比較例において、それぞれ、硬化性樹脂組成物又は比較用組成物をガラス容器に入れて密閉し、25℃、遮光の環境下に14日間静置した後、経時前膜厚を求めたときと同じ回転数を用いて、硬化性樹脂組成物又は比較用組成物をスピンコート法でシリコンウェハ上に適用して硬化性樹脂組成物層を形成した。得られた硬化性樹脂組成物層を適用したシリコンウェハをホットプレート上で、100℃で5分間乾燥し、シリコンウェハ上に均一な厚さの硬化性樹脂組成物層を得た。得られた硬化性樹脂組成物層の膜厚を上記経時前膜厚の測定方法における膜厚の測定方法と同様の方法によって測定し、この値を経時後膜厚とした。 -Measurement of film thickness after aging-
In each Example and Comparative Example, the curable resin composition or the comparative composition was placed in a glass container, sealed, and allowed to stand in a light-shielded environment at 25 ° C. for 14 days, and then the pre-aging film thickness was determined. A curable resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method at the same number of revolutions as in the case of the above to form a curable resin composition layer. The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a curable resin composition layer having a uniform thickness on the silicon wafer. The film thickness of the obtained curable resin composition layer was measured by the same method as the film thickness measuring method in the above-mentioned pre-aging film thickness measuring method, and this value was taken as the post-aging film thickness.
以下の式により、膜厚変化率を算出した。
膜厚変化率 (%) = |経時前膜厚-経時後膜厚|/経時前膜厚×100
算出された膜厚変化率を下記評価基準に従って評価し、評価結果を表2~表8の「保存安定性評価」の欄に記載した。上記膜厚変化率が小さいほど、硬化性樹脂組成物は保存安定性に優れるといえる。 -Film thickness change rate-
The film thickness change rate was calculated by the following formula.
Film thickness change rate (%) = | Pre-aging film thickness-Post-aging film thickness | / Pre-aging film thickness x 100
The calculated film thickness change rate was evaluated according to the following evaluation criteria, and the evaluation results are shown in the "Storage stability evaluation" column of Tables 2 to 8. It can be said that the smaller the rate of change in film thickness, the better the storage stability of the curable resin composition.
A:上記膜厚変化率が10%未満であった。
B:上記膜厚変化率が10%以上15%未満であった。
C:上記膜厚変化率が15%以上であった。 -Evaluation criteria-
A: The rate of change in film thickness was less than 10%.
B: The rate of change in film thickness was 10% or more and less than 15%.
C: The film thickness change rate was 15% or more.
比較例1~2に係る比較用組成物は、トリアゾール構造を有する化合物を含むが、pHが7.0以上である。この比較例1~2に係る比較用組成物は、硬化膜が隣接する金属の腐食の抑制及び液保存安定性に劣ることがわかる。
比較例3~4に係る比較用組成物は、トリアゾール構造を有する化合物を含まず、かつ、pHが7.0以上である。この比較例1~2に係る比較用組成物は、硬化膜が隣接する金属の腐食の抑制及び液保存安定性に劣ることがわかる。
比較例5に係る比較用組成物は、pHが7.0未満であるが、トリアゾール構造を有する化合物を含まない。この比較例5に係る比較用組成物は、硬化膜が隣接する金属の腐食の抑制に劣ることがわかる。 From the above results, a composition containing at least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof, a compound having a triazole structure, and a solvent according to the present invention. According to the curable resin composition having a pH of less than 7.0, it can be seen that a cured film having excellent suppression of corrosion of adjacent metals can be obtained.
The comparative compositions according to Comparative Examples 1 and 2 contain a compound having a triazole structure, and have a pH of 7.0 or higher. It can be seen that the comparative compositions according to Comparative Examples 1 and 2 are inferior in suppressing corrosion of the metal adjacent to the cured film and in liquid storage stability.
The comparative compositions according to Comparative Examples 3 to 4 do not contain a compound having a triazole structure and have a pH of 7.0 or higher. It can be seen that the comparative compositions according to Comparative Examples 1 and 2 are inferior in suppressing corrosion of the metal adjacent to the cured film and in liquid storage stability.
The comparative composition according to Comparative Example 5 has a pH of less than 7.0, but does not contain a compound having a triazole structure. It can be seen that the comparative composition according to Comparative Example 5 is inferior in suppressing corrosion of the metal adjacent to the cured film.
実施例1において使用した硬化性樹脂組成物を、表面に銅薄層が形成された樹脂基材の銅薄層の表面にスピンコート法により層状に適用して、100℃で5分間乾燥し、膜厚20μmの硬化性樹脂組成物層を形成した後、ステッパー((株)ニコン製、NSR1505 i6)を用いて露光した。露光はマスク(パターンが1:1ラインアンドスペースであり、線幅が10μmであるバイナリマスク)を介して、波長365nmの光を照射して行った。露光の後、シクロペンタノンで30秒間現像し、PGMEAで20秒間リンスし、層のパターンを得た。
次いで、230℃で3時間加熱し、再配線層用層間絶縁膜を形成した。この再配線層用層間絶縁膜は、絶縁性に優れていた。
また、これらの再配線層用層間絶縁膜を使用して半導体デバイスを製造したところ、問題なく動作することを確認した。 <Example 101>
The curable resin composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin base material having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 5 minutes. After forming a curable resin composition layer having a thickness of 20 μm, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). The exposure was performed by irradiating light having a wavelength of 365 nm through a mask (a binary mask having a pattern of 1: 1 line and space and a line width of 10 μm). After exposure, it was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a layer pattern.
Then, it was heated 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.
Claims (14)
- ポリイミド、ポリベンゾオキサゾール、及びこれらの前駆体よりなる群から選ばれた少なくとも1種の樹脂、
トリアゾール構造を有する化合物、並びに、
溶剤を含み、
組成物のpHが7.0未満である
硬化性樹脂組成物。 At least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.
Compounds having a triazole structure, as well as
Contains solvent,
A curable resin composition in which the pH of the composition is less than 7.0. - 前記トリアゾール構造を有する化合物のジメチルスルホキシド中のpKaが15未満である、請求項1に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, wherein the pKa in dimethyl sulfoxide of the compound having a triazole structure is less than 15.
- 前記トリアゾール構造を有する化合物が1,2,3-トリアゾール構造を有する化合物を含む、請求項1又は2に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1 or 2, wherein the compound having a triazole structure contains a compound having a 1,2,3-triazole structure.
- 前記トリアゾール構造を有する化合物がベンゾトリアゾール構造を有する化合物を含む、請求項1~3のいずれか1項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 3, wherein the compound having a triazole structure contains a compound having a benzotriazole structure.
- 前記樹脂100質量部に対し、感光剤1~40質量部と、前記トリアゾール構造を有する化合物0.05~20質量部と、前記溶剤50~300質量部とを含む、請求項1~4のいずれか1項に記載の硬化性樹脂組成物。 Any of claims 1 to 4, which comprises 1 to 40 parts by mass of a photosensitizer, 0.05 to 20 parts by mass of the compound having a triazole structure, and 50 to 300 parts by mass of the solvent with respect to 100 parts by mass of the resin. The curable resin composition according to item 1.
- 前記溶剤として、窒素原子を含まない溶剤を含む、請求項1~5のいずれか1項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 5, which contains a solvent containing no nitrogen atom as the solvent.
- 前記溶剤として、炭素原子、酸素原子及び水素原子のみから構成される溶剤を含む、請求項1~6のいずれか1項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 6, wherein the solvent contains a solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms.
- 再配線層用層間絶縁膜の形成に用いられる、請求項1~7のいずれか1項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 7, which is used for forming an interlayer insulating film for a rewiring layer.
- 請求項1~8のいずれか1項に記載の硬化性樹脂組成物を硬化してなる硬化膜。 A cured film obtained by curing the curable resin composition according to any one of claims 1 to 8.
- 請求項9に記載の硬化膜を2層以上含み、前記硬化膜同士のいずれかの間に金属層を含む積層体。 A laminate containing two or more layers of the cured film according to claim 9 and containing a metal layer between any of the cured films.
- 請求項1~8のいずれか1つに記載の硬化性樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。 A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of claims 1 to 8 to a substrate to form a film.
- 前記膜を露光する露光工程及び前記膜を現像する現像工程を含む、請求項11に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 11, further comprising an exposure step of exposing the film and a developing step of developing the film.
- 前記膜を50~450℃で加熱する加熱工程を含む、請求項11又は12に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 11 or 12, which comprises a heating step of heating the film at 50 to 450 ° C.
- 請求項9に記載の硬化膜又は請求項10に記載の積層体を含む、半導体デバイス。 A semiconductor device comprising the cured film according to claim 9 or the laminate according to claim 10.
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