WO2020262228A1 - 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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- WO2020262228A1 WO2020262228A1 PCT/JP2020/024109 JP2020024109W WO2020262228A1 WO 2020262228 A1 WO2020262228 A1 WO 2020262228A1 JP 2020024109 W JP2020024109 W JP 2020024109W WO 2020262228 A1 WO2020262228 A1 WO 2020262228A1
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/145—Polyamides; Polyesteramides; Polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
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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
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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
- G03F7/40—Treatment after imagewise removal, e.g. baking
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.
- Polymer precursors such as polyimide resin, polyamideimide resin, and polybenzoxazole resin are collectively referred to as "heterocycle-containing polymer precursor”.
- the resin obtained by cyclizing (also referred to as) is excellent in heat resistance, insulating property, and the like, and is therefore applied to various uses.
- the above application is not particularly limited, and examples of a semiconductor device for mounting include use as a material for an insulating film or a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.
- the heterocycle-containing polymer precursor is used in the form of a curable resin composition containing the heterocycle-containing polymer precursor.
- a curable resin composition is applied to a base material by, for example, coating, and then the heterocyclic-containing polymer precursor is cyclized by heating or the like to form a cured resin on the base material.
- 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 heterocyclic-containing polymer precursors is expected more and more.
- Patent Document 1 describes a polyimide precursor composition containing a polyimide precursor, a thermobase generator that generates a base by heat, and a solvent, wherein the polyimide precursor is a repeating unit having a specific structure.
- a polyimide precursor composition which is a neutral compound which causes thermal decomposition by heating at a temperature of 200 ° C. or lower to generate a secondary amine is described. There is.
- curable resin composition containing a heterocyclic-containing polymer precursor, it is desired to provide a curable resin composition having excellent storage stability of the composition and film strength of the obtained cured product.
- the present invention relates to a curable resin composition having excellent storage stability of the composition and the film strength of the obtained cured film, a cured film obtained by curing the curable resin composition, and a laminate containing the cured film. It is an object of the present invention to provide a method for producing the cured film and a semiconductor device including the cured film or the laminate.
- ⁇ 1> At least one resin selected from the group consisting of a polyimide precursor, a polyamide-imide precursor, and a polybenzoxazole precursor, and A curable resin composition containing a compound having a structure represented by the following formula (1-1).
- Ar represents an aromatic heterocyclic structure
- * is an aromatic ring structure, an aliphatic ring structure, a linear or branched unsaturated hydrocarbon structure, or a linear or branched structure.
- ⁇ 2> The curable resin composition according to ⁇ 1>, wherein Ar in the above formula (1-1) has a 5-membered ring structure.
- X 1 represents an n-valent organic group
- RC is a hydrogen atom, an alkyl group, or an aryl.
- 2 or more of Z 1 to Z 4 are -CR C.
- 2 or more RCs may be combined to form a ring structure
- n represents an integer of 1 to 10
- n is 2 or more, 2 or more Z 1 to Z 4 are.
- Each may be the same or different.
- ⁇ 5> The curable resin composition according to ⁇ 4>, wherein X 1 contains an aromatic hydrocarbon ring structure.
- ⁇ 6> The curable resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the compound having the structure represented by the above formula (1-1) has a molecular weight of 90 to 500.
- ⁇ 7> The curable resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the compound having the structure represented by the above formula (1-1) is a thermosetting agent.
- ⁇ 8> The curable resin composition according to any one of ⁇ 1> to ⁇ 7>, further comprising a photopolymerization initiator and a polymerizable compound.
- ⁇ 9> The curable resin composition according to any one of ⁇ 1> to ⁇ 8>, which is used for forming an interlayer insulating film for a rewiring layer.
- ⁇ 10> A cured film obtained by curing the curable resin composition according to any one of ⁇ 1> to ⁇ 9>.
- ⁇ 11> A laminate containing two or more layers of the cured film according to ⁇ 10> and containing a metal layer between any of the cured films.
- ⁇ 12> 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 ⁇ 9> to a substrate to form a film.
- ⁇ 13> The method for producing a cured film according to ⁇ 12>, which comprises an exposure step of exposing the film and a developing step of developing the film.
- ⁇ 14> The method for producing a cured film according to ⁇ 12> or ⁇ 13>, which comprises a heating step of heating the film at 50 to 450 ° C.
- a semiconductor device comprising the cured film according to ⁇ 10> or the laminate according to ⁇ 11>.
- a curable resin composition having excellent storage stability of the composition and the film strength of the obtained cured film, a cured film obtained by curing the curable resin composition, and a laminate containing the cured film.
- a body, a method for producing the 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 using the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
- the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
- the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
- the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
- (meth) acrylate means both “acrylate” and “methacrylate”, or either
- (meth) acrylic means both “acrylic” and “methacrylic", or
- (meth) acryloyl means both “acryloyl” and “methacrylic", or either.
- Me in the structural formula represents a methyl group
- Et represents an ethyl group
- Bu represents a butyl group
- Ph represents a phenyl group.
- the total solid content means the total mass of all the components of the composition excluding the solvent.
- the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
- GPC measurement gel permeation chromatography
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
- the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as “upper”.
- the opposite direction is referred to as "down”.
- the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component.
- the content of each component in the composition means the total content of all the compounds corresponding to the component.
- the temperature is 23 ° C. and the atmospheric pressure is 101,325 Pa (1 atm).
- the combination of preferred embodiments is a more preferred embodiment.
- the curable resin composition of the present invention is represented by at least one resin selected from the group consisting of a polyimide precursor, a polyamide-imide precursor, and a polybenzoxazole precursor, and the following formula (1-1). Includes compounds that have the structure to be. Further, the curable resin composition of the present invention preferably further contains a photopolymerization initiator and a polymerizable compound.
- Ar represents an aromatic heterocyclic structure
- * is an aromatic ring structure, an aliphatic ring structure, a linear or branched unsaturated hydrocarbon structure, or a linear or branched structure. Represents a binding site with a branched saturated hydrocarbon structure.
- the curable resin composition of the present invention is excellent in storage stability of the composition and the film strength of the obtained cured film.
- the mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
- the curable resin composition of the present invention contains a compound having a structure represented by the formula (1-1). It is considered that the above compound traps the amine compound in the curable resin composition during storage at a low temperature, thereby improving the storage stability of the composition. Further, during curing of the polymer precursor such as during heating, the cyclization rate of the heterocyclic polymer precursor is generated by generating a base such as a trapped amine compound or a basic aromatic compound from the above compound.
- the film strength of the obtained cured film is improved.
- a curable resin composition containing a polymer precursor for example, when a curable resin composition is further applied on the cured film and cured to prepare a laminate.
- the cured film formed earlier may come into contact with the developer or other composition. Therefore, in the curable resin composition, for example, from the viewpoint of resistance of the cured film to a developing solution or suppression of dissolution of the cured film due to contact with other compositions, the obtained cured film is cured with excellent chemical resistance. It is desired to provide a sex resin composition.
- the curable resin composition of the present invention since the cyclization rate of the heterocyclic polymer precursor in the cured film is increased by the above mechanism, it is considered that the cured film is likely to have excellent chemical resistance.
- Patent Document 1 does not describe or suggest a curable resin composition containing a compound having a structure represented by the formula (1-1).
- the components contained in the curable resin composition of the present invention will be described in detail.
- the curable resin composition of the present invention contains a heterocyclic polymer precursor.
- the curable resin composition of the present invention contains at least one precursor selected from the group consisting of a polyimide precursor, a polyamide-imide precursor and a polybenzoxazole precursor as the heterocycle-containing polymer precursor, and is a polyimide. It preferably contains a precursor.
- polyimide precursor, polyamide-imide precursor From the viewpoint of the film strength of the obtained cured film, the polyimide precursor or the polyamide-imide precursor preferably has a repeating unit represented by the following formula (1).
- a 1 and A 2 each independently represent an oxygen atom or -NH-
- R 111 represents a divalent organic group
- R 115 represents a tetravalent organic group
- R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
- -A 1 and A 2- A 1 and A 2 in the formula (1) independently represent an oxygen atom or -NH-, and an oxygen atom is preferable.
- -R 111- R 111 in the formula (1) represents a divalent organic group.
- the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are combined, and the number of carbon atoms is exemplified.
- the group combined as described above is preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.
- R 111 in formula (1) is preferably derived from diamine.
- diamine used for producing the polyimide precursor or the polyamide-imide 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.
- the diamine is a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or these. It is preferably a diamine containing two or more combined groups, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms.
- aromatic groups include:
- diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane or isophoronediamine; meta or paraphenylenediamine, diaminotoluene, 4,4'-or 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether,
- diamines (DA-1) to (DA-18) shown below are also preferable.
- a diamine having at least two alkylene glycol units in the main chain is also mentioned as a preferable example.
- a diamine containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule is preferable, and a diamine containing no aromatic ring is preferable.
- Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, and Jeffamine (registered trademark).
- EDR-148 Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2)) -Aminopropoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propane-2-amine, etc., but are limited to these. Not done.
- x, y, and z are arithmetic mean values.
- Ar 0 is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and a phenylene group is preferable.
- the preferred range of L 0 is synonymous with A above.
- R 111 in the formula (1) is preferably a divalent organic group represented by the following formula (51) or the formula (61) from the viewpoint of i-ray transmittance.
- a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.
- R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, a fluoromethyl group, It is a difluoromethyl group or a trifluoromethyl group, and * independently represents a binding site with another structure.
- the monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
- R 58 and R 59 are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups, or trifluoromethyl groups, respectively.
- Examples of the diamine compound giving the structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2. Examples thereof include'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. One of these may be used, or two or more thereof may be used in combination.
- -R 115- R 115 in the formula (1) 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.
- R 112 is synonymous with A and has the same preferred range. * Independently represent a binding site with another structure.
- tetravalent organic group represented by R 115 in the formula (1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
- the tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
- R 115 represents a tetravalent organic group.
- R 115 has the same meaning as R 115 in formula (1).
- tetracarboxylic dianhydride examples include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride (4,4'-biphthal).
- DAA-1 to DAA-5 tetracarboxylic dianhydrides
- DAA-5 tetracarboxylic dianhydrides
- R 113 and R 114- R 113 and R 114 in the formula (1) independently represent a hydrogen atom or a monovalent organic group. At least one of R 113 and R 114 preferably contains a radically polymerizable group, and more preferably both contain a radically polymerizable group.
- the radically polymerizable group include a group capable of a cross-linking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond.
- Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acryloyl group, and the following formula ( Examples thereof include groups represented by III).
- R200 represents a hydrogen atom or a methyl group, and a methyl group is preferable.
- R 201 is an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom).
- ⁇ 12 is preferable, 1 to 6 is more preferable, 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, 1 to 6 is more preferable, and 1 to 3 is particularly preferable).
- the (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
- R 201 examples include 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-, and more preferably an ethylene group, a propylene group, a trimethylene group, and -CH 2 CH (OH) CH 2- .
- R 200 is a methyl group and R 201 is an ethylene group.
- * represents a binding site with another structure.
- a preferred embodiment of the polyimide or polyamideimide precursor in the present invention is an aliphatic group having 1, 2 or 3 or preferably 1 acid group as the monovalent organic group of R 113 or R 114 .
- Examples include aromatic groups and arylalkyl groups. Specific examples thereof include an aromatic group having an acid group having 6 to 20 carbon atoms and an arylalkyl group having an acid group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned.
- the acid group is preferably a hydroxy group. That is, R 113 or R 114 is preferably a group having a hydroxy group.
- a substituent that improves the solubility of the developing solution is preferably used.
- R 113 or R 114 is a hydrogen atom, a benzyl group, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group or a 4-hydroxybenzyl group from the viewpoint of solubility in an aqueous developer.
- R 113 or R 114 is preferably a monovalent organic group.
- a monovalent organic group a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group is preferable, and an alkyl group substituted with an aromatic group is more preferable.
- the alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group).
- the alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and octadecyl group.
- 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 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.
- an alkyl group substituted with an aromatic group a linear alkyl group substituted with an aromatic group described below is preferable.
- aromatic group examples include a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an inden ring, and azulene.
- the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an inden ring, and azulene.
- the cyclic structure constituting the group includes a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolin ring, an indol ring, and a benzofuran.
- Ring benzothiophene ring, isobenzofuran ring, quinolysin ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, aclysin ring, phenanthrene ring, thianthrene ring, chromene ring. , Xanthene ring, phenoxatiin ring, phenothiazine ring or phenazine ring).
- the polyimide precursor or the polyamide-imide precursor has a fluorine atom in the repeating unit.
- the fluorine atom content in the polyimide precursor or the polyamide-imide precursor is preferably 10% by mass or more, more preferably 20% by mass or more. There is no particular upper limit, but 50% by mass or less is practical.
- an aliphatic group having a siloxane structure may be copolymerized in a repeating unit represented by the formula (1).
- the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
- the repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1-A) or the formula (1-B).
- a 11 and A 12 represent an oxygen atom or -NH-
- R 111 and R 112 each independently represent a divalent organic radical
- R 113 and R 114 independently represent a hydrogen atom or 1 Representing a valent organic group
- at least one of R 113 and R 114 is preferably a group containing a radically polymerizable group, and more preferably a radically polymerizable group.
- a 11 , A 12 , R 111 , R 113 and R 114 are synonymous with the preferred ranges of A 1 , A 2 , R 111 , R 113 and R 114 in formula (1), respectively.
- R 112 has the same meaning as R 112 in formula (5), and more preferably among others oxygen atoms.
- the bonding position of the carbonyl group to the benzene ring in the formula is preferably 4, 5, 3', 4'in the formula (1-A). In formula (1-B), it is preferably 1, 2, 4, 5.
- the repeating unit represented by the formula (1) may be one kind, or two or more kinds. Further, it may contain a structural isomer of a repeating unit represented by the formula (1). Further, the polyimide precursor or the polyamide-imide precursor may include other types of repeating units in addition to the repeating unit of the above formula (1).
- the heterocyclic-containing polymer precursor is a polyamide-imide precursor
- the polyamide-imide precursor may further contain a repeating unit represented by the following formula (PAI-1).
- R 116 represents a divalent organic group and R 111 represents a divalent organic group.
- R 116 is composed of a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a single bond or a linking group. Examples of the above-mentioned linked groups include a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
- the aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group.
- a group in which two or more of the above are combined is more preferable.
- the group is preferable, and —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
- an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
- halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
- the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
- the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom.
- preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
- arylene group a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
- R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
- a compound having two carboxy groups is called a dicarboxylic acid compound
- a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound.
- the carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
- Examples of the halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids. Examples include aciddihalide compounds. Only one kind or two or more kinds of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used.
- the dicarboxylic acid compound or the dicarboxylic acid dihalide compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic fat having 3 to 20 carbon atoms.
- a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group group, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms is preferable.
- a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferable.
- aromatic groups include the above-mentioned AR-1 to AR-10.
- dicarboxylic acid compound examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-.
- R 111 has the same meaning as R 111 in the above equation (1), a preferable embodiment thereof is also the same.
- the polyamide-imide precursor may further contain a repeating unit represented by the following formula (PAI-2).
- PAI-2 R 117 represents a trivalent organic group
- R 111 represents a divalent organic group
- a 2 represents an oxygen atom or -NH-
- R 113 represents a hydrogen atom or monovalent. Represents an organic group of.
- R 117 is composed of linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, heteroaromatic groups, or single-bonded or linked groups.
- Examples of the above-mentioned linked groups include a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
- the aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable.
- a group in which two or more of the above are combined is more preferable.
- the group is preferable, and —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
- an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
- halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
- the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
- the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom.
- preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
- arylene group a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
- R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. Chlorination is preferable as the halogenation.
- a compound having three carboxy groups is referred to as a tricarboxylic acid compound. Of the three carboxy groups of the tricarboxylic acid compound, two carboxy groups may be acid anhydrideized.
- the halogenated tricarboxylic acid compound used in the production of the polyamide-imide precursor include branched chain aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. Only one kind of these tricarboxylic acid compounds may be used, or two or more kinds may be used.
- the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a carbon number of carbon atoms.
- a tricarboxylic acid compound containing 6 to 20 aromatic groups or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or carbon by a single bond or a linking group is preferable.
- a tricarboxylic acid compound containing a group in which two or more aromatic groups of several 6 to 20 are combined is more preferable. Examples of aromatic groups include the above-mentioned AR-1 to AR-10.
- the tricarboxylic acid compound examples include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid.
- Or phthalic acid anhydride and benzoic acid are single-bonded, with -O-, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- or phenylene group. Examples thereof include linked compounds.
- These compounds may be compounds in which two carboxy groups are anhydrated (eg, trimellitic acid anhydride) or compounds in which at least one carboxy group is halogenated (eg, trimellitic acid chloride). There may be.
- each R 111, A 2, R 113 have the same meaning as R 111, A 2, R 113 in the above equation (1), a preferable embodiment thereof is also the same.
- the polyimide precursor in the present invention 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units are the repeating units represented by the formula (1). Is exemplified. As an upper limit, 100 mol% or less is practical.
- the repeating unit represented by the formula (1), the repeating unit represented by the formula (PAI-1), and the formula (PAI-2). The total content of the repeating unit is 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more, and the polyamide-imide precursor is exemplified. As an upper limit, 100 mol% or less is practical.
- the weight average molecular weight (Mw) of the polyimide precursor or the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50. It is 000.
- the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
- the degree of dispersion of the molecular weight of the polyimide precursor or the polyamide-imide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
- the degree of molecular weight dispersion means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).
- the polyimide precursor or polyamide-imide precursor 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 and then reacting it with a diamine.
- 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-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.
- the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
- the polybenzoxazole precursor preferably contains a repeating unit represented by the following formula (2).
- R 121 represents a divalent organic group
- R 122 represents a tetravalent organic group
- R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group. Represent.
- R 121 represents a divalent organic group.
- the divalent organic group includes an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, 6 to 14 carbon atoms). Is more preferable, and 6 to 12 is particularly preferable).
- the aromatic group constituting R 121 include R 111 of the above formula (1).
- the aliphatic group a linear aliphatic group is preferable.
- R 121 is preferably derived from 4,4'-oxydibenzoyl chloride.
- R 122 represents a tetravalent organic group.
- the tetravalent organic group has the same meaning as R 115 in the above formula (1), and the preferable range is also the same.
- R 122 is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
- R -R 123 and R 124- R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R 113 and R 114 in the above formula (1), and the preferable range is also the same.
- the polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units of the above formula (2).
- the polybenzoxazole precursor further contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.
- SL diamine residue represented by the following formula (SL) as another type of repeating unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.
- R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R 2s.
- Is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of R 3s , R 4s , R 5s , and R 6s is aromatic. It is a group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and the rest is a hydrogen atom or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms).
- the a structure and the b structure may be block polymerization or random polymerization.
- the a structure is 5 to 95 mol%
- the b structure is 95 to 5 mol%
- a + b is 100 mol%.
- 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 molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight in the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be lowered, and the effect of suppressing warpage and the effect of improving solubility can be achieved at the same time.
- the tetracarboxylic dianhydride is further provided in that it improves the alkali solubility of the curable resin composition. It is preferable that the tetracarboxylic acid residue remaining after the removal of the acid dianhydride group from the product is contained as a repeating unit. Examples of such a tetracarboxylic acid residue include the example of R 115 in the formula (1).
- the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. is there.
- the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
- the degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
- the acid value of the heterocyclic polymer precursor is preferably 1 mmol / g or less, more preferably 0.5 mmol / g or less, and 0. More preferably, it is 3 mmol / g or less.
- the lower limit of the acid value is not particularly limited, and may be 0 mmol / g or more.
- the acid value of the heterocyclic polymer precursor is preferably 1 to 8 mmol / g, more preferably 1.5 to 6 mmol / g. It is more preferably 2 to 5 mmol / g.
- the acid value of the heterocyclic polymer precursor refers to the amount (mmol) of acid groups contained in 1 g of the heterocyclic polymer precursor.
- the acid group refers to a group that is neutralized by an alkali having a pH of 12 or higher (for example, sodium hydroxide). Further, the acid group is preferably a group having a pKa of 10 or less.
- the acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
- the content of the heterocycle-containing polymer precursor in the curable resin composition of the present invention is preferably 20% by mass or more, preferably 30% by mass or more, based on the total solid content of the curable resin composition. More preferably, it is more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and further preferably 70% by mass or more.
- the content of the heterocycle-containing polymer precursor in the curable resin composition of the present invention is preferably 99.5% by mass or less, preferably 99% by mass, based on the total solid content of the curable resin composition. The following is more preferable, 98% by mass or less is further preferable, 97% by mass or less is further preferable, and 95% by mass or less is further preferable.
- the curable resin composition of the present invention may contain only one type of heterocyclic polymer precursor, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
- the curable resin composition of the present invention contains a compound having a structure represented by the formula (1-1) (hereinafter, also referred to as “specific compound”).
- the specific compound is preferably a thermal base generator.
- the specific compound is a thermosetting agent when a layer formed by the curable resin composition of the present invention (preferably, the curable resin composition of the present invention containing a solvent is applied to a base material. It means that the specific compound is a compound that generates a base when the layer (the layer from which at least a part of the solvent is removed) is heated by heating at a temperature of 100 ° C. or the like.
- the specific compound is preferably a compound having a decomposition rate of 50 mol% or more by heating at 230 ° C.
- the specific compound is preferably a compound having a decomposition rate of 10 mol% or less by heating at 100 ° C. for 3 hours.
- the decomposition rate is measured by the following method.
- the curable resin composition is applied onto glass and dried by heating at 100 ° C. for 1 minute to form a curable resin composition layer.
- the amount of the curable resin composition applied is such that the film thickness after drying is 15 ⁇ m. Then, when measuring the decomposition rate of the curable resin composition layer by heating at 230 ° C. for 3 hours, for example, heating at 230 ° C.
- the specific compound is preferably a compound that generates a base by heating in a heating step described later.
- the decomposition temperature of the specific compound in the curable resin composition is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 120 ° C. or higher, and further preferably 140 ° C. or higher. preferable. As the upper limit, it is more preferably 450 ° C. or lower, more preferably 350 ° C. or lower, and further preferably 250 ° C. or lower.
- the decomposition temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when the solid content of the curable resin composition is heated to 500 ° C. in a pressure-resistant capsule at 5 ° C./min. Examples of the device used for measuring the decomposition temperature include Q2000 (manufactured by TA Instruments) and the like.
- the pKa of the conjugate acid of the base generated from the specific compound is preferably 8 or more, and more preferably 9 or more, from the viewpoint of the film strength of the obtained cured film. It is preferable, and more preferably 10 or more.
- the upper limit of the pKa is not particularly limited, but is preferably 16 or less.
- the term "pKa” as used herein means a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is represented by its negative common logarithm pKa. The smaller the pKa, the stronger the acid. Unless otherwise specified, pKa is a value calculated by ACD / ChemSketch (registered trademark).
- the pKa of the compound means the maximum value among the plurality of pKa in the compound, unless otherwise specified.
- Ar represents an aromatic heterocyclic structure.
- the aromatic heterocyclic structure represented by Ar is a 5-membered ring structure such as a pyrazole ring structure, a pyrazole ring structure, an imidazole ring structure, a triazole ring structure or a tetrazole ring structure, a 9-membered ring structure such as an azonin ring, or an indole.
- a polycyclic ring structure such as a ring structure, an isoindole ring structure, a benzimidazole ring structure, an indazole ring structure, a benzotriazole ring structure, a purine ring structure, and a carbazole ring structure is preferable, and a 5-membered ring structure is preferable. It is more preferably a pyrazole ring structure, an imidazole ring structure, a triazole ring structure, or a tetrazole ring structure, and particularly preferably a pyrazole ring structure, an imidazole ring structure, or a triazole ring structure.
- One of the nitrogen atoms contained in these aromatic heterocyclic structures is the nitrogen atom represented by the formula (1-1).
- the heterocyclic structure represented by Ar is the polycyclic ring structure, an indazole ring structure or a benzimidazole ring structure is preferable.
- * indicates an aromatic ring structure, an aliphatic ring structure, a linear or branched unsaturated hydrocarbon structure, or a linear or branched saturated hydrocarbon structure.
- the above aromatic ring structure, aliphatic ring structure, linear or branched unsaturated hydrocarbon structure, or linear or branched saturated hydrocarbon structure is within the range in which the effect of the present invention can be obtained.
- Each may have a substituent. That is, the position where it is bonded to * in the partial structure represented by the formula (1-1) is an aromatic ring structure, an aliphatic ring structure, a linear or branched unsaturated hydrocarbon structure, or a linear structure.
- the aromatic ring structure is preferably an aromatic hydrocarbon ring structure, more preferably an aromatic hydrocarbon ring structure having 6 to 20 carbon atoms, and even more preferably a benzene ring structure.
- the aliphatic ring structure is preferably an aliphatic hydrocarbon ring structure having 6 to 20 carbon atoms, more preferably a saturated aliphatic hydrocarbon ring structure having 6 to 20 carbon atoms, and a cyclopentane ring structure or a cyclohexane ring.
- a monocyclic saturated aliphatic hydrocarbon ring structure such as a structure, or a crosslinked saturated aliphatic hydrocarbon ring structure such as a Bornan ring structure, an isobornan ring structure, an adamantan ring structure, or a dicyclopentane ring structure is more preferable, and a cyclohexane ring or an adamantyl is more preferable. Rings are more preferred.
- As the linear or branched unsaturated hydrocarbon structure an ethynyl group or an isopropenyl group is preferable, and an isopropenyl group is more preferable.
- As the saturated hydrocarbon structure a saturated hydrocarbon structure having 1 to 20 carbon atoms is preferable, and a saturated hydrocarbon structure having 1 to 4 carbon atoms is more preferable.
- the structure represented by the above formula (1-1) is preferably a structure represented by the following formula (1-2).
- the 5-membered ring structure containing Z 1 to Z 4 is preferably a triazole ring, a pyrazole ring or an imidazole ring, more preferably a pyrazole ring or an imidazole ring, and further preferably an imidazole ring.
- the 5-membered ring structure containing Z 1 to Z 4 is preferably a triazole ring, a pyrazole ring or an imidazole ring, preferably a triazole ring or a pyrazole ring, and more preferably a triazole ring.
- Alkyl groups are more preferred, and hydrogen atoms are even more preferred.
- the alkyl group in R c is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
- the hydrogen atom in the alkyl group may be substituted with a known substituent such as a halogen atom within the range in which the effect of the present invention can be obtained.
- Aryl group in R c is preferably an aryl group having 6 to 20 carbon atoms, a phenyl group is more preferable.
- the hydrogen atom in the aryl group may be substituted with a known substituent within the range in which the effect of the present invention can be obtained.
- Amino group in R c is optionally substituted by a known substituent. For example, a dialkylamino group, a diarylamino group and the like can be mentioned.
- the preferred embodiment of the alkyl group in the dialkylamino group is the same as the preferred embodiment of the alkyl group in RC described above.
- a preferred embodiment of the aryl group in the diarylamino group are the same as the preferred embodiment of the aryl group in the above R c.
- a preferred embodiment of the alkyl group in the alkyloxycarbonyl group for R c is the same as the preferred embodiment of the alkyl group in the above R c.
- the ring structure to be formed is preferably an aromatic hydrocarbon ring or an aromatic heterocycle, more preferably an aromatic hydrocarbon ring, and even more preferably a benzene ring.
- the aromatic heterocycle is preferably an aromatic heterocycle having a nitrogen atom as a complex atom.
- the number of ring members of the aromatic heterocycle is preferably 5 or 6, and more preferably 6. Further, from the viewpoint of storage stability, a mode in which two or more Rc do not form a ring structure is also a preferable mode.
- the specific compound is preferably a compound represented by the following formula (1-3).
- X 1 represents an n-valent organic group
- RC is a hydrogen atom, an alkyl group, or an aryl.
- 2 or more RCs may be combined to form a ring structure
- n represents an integer of 1 to 10
- n is 2 or more, 2 or more Z 1 to Z 4 are.
- Each may be the same or different.
- X 1 represents a monovalent organic group, preferably an alkyl group, an aryl group, or a (meth) acryloyl group, and a cyclic alkyl group, More preferably, it is an aryl group or a (meth) acryloyl group.
- aliphatic hydrocarbon group or "alkyl group”
- alkyl group an alkyl group having 1 to 20 carbon atoms is preferable, a cyclic alkyl group having 6 to 20 carbon atoms is more preferable, and a cyclohexyl group or an adamantyl group is further preferable.
- aryl group a phenyl group is more preferable.
- X 1 represents an organic group having a valence of 2 or more, and is a group obtained by removing n hydrogen atoms from the aliphatic ring structure or the aromatic ring structure. More preferably, it is a group obtained by removing n hydrogen atoms from the aliphatic hydrocarbon ring structure or the aromatic hydrocarbon ring structure, and n hydrogen atoms are removed from the aromatic hydrocarbon ring structure. It is more preferably a hydrocarbon group.
- the aliphatic ring structure an aliphatic saturated hydrocarbon ring structure such as a cyclohexane ring is preferable.
- aromatic ring structure a benzene ring structure is preferable.
- X 1 may be an aliphatic ring structure or a group in which two or more aromatic ring structures are bonded.
- a group represented by the following formula (X-1) is preferable.
- L 1 represents a single bond or a b-valent linking group
- a represents an integer of 1 to 5
- b represents an integer of 2 or more
- the RN is a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and more preferably a hydrogen atom or a methyl group.
- a hydrogen atom is particularly preferable.
- the aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms. It is more preferably a group.
- the aliphatic hydrocarbon group may have a substituent, and examples of the substituent include an aromatic hydrocarbon group and a halogen atom.
- the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 carbon atoms. It is more preferably a hydrogen group.
- the aromatic hydrocarbon group may have a substituent, and examples of the substituent include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a halogen atom.
- a represents an integer of 1 to 5, preferably 1 or 2, and more preferably 1.
- b is preferably an integer of 2 to 10, more preferably an integer of 2 to 6, and more preferably 2 or 3.
- X 1 is preferably a phenyl group.
- X 1 is preferably a structure obtained by removing 2 or more hydrogen atoms from the benzene ring structure, or a group represented by the above formula (X-1) as the above aromatic hydrocarbon ring structure.
- Z 1 ⁇ Z 4 and R C are each the same meaning as Z 1 ⁇ Z 4 and R C in formula (1-2), preferable embodiments thereof are also the same.
- n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.
- the molecular weight of the specific compound is preferably 90 to 2,000, more preferably 90 to 1,000, further preferably 90 to 500, and 100. It is particularly preferably about 400.
- Specific examples of the specific compound include, but are not limited to, the anion moiety in the compounds represented by the following formulas (BG-1) to (BG-16).
- the content of the specific compound is 0.005 to 50% by mass with respect to the total solid content of the curable resin composition from the viewpoint of improving the storage stability of the composition and the elongation at break of the obtained cured film.
- the lower limit is more preferably 0.05% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.
- the upper limit is more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less, from the viewpoint of corrosion resistance of a metal (for example, copper used for wiring or the like).
- the content of the specific compound with respect to 100 parts by mass of the heterocyclic polymer precursor is 0.005 parts by mass or more from the viewpoint of improving the storage stability of the composition and the elongation at break of the obtained cured film. It is preferably 0.06 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 1 part by mass or more. From the viewpoint of corrosion resistance of metal (for example, copper used for wiring and the like), the upper limit is preferably, for example, 20 parts by mass or less, more preferably 15 parts by mass or less, and 10 parts by mass. It is more preferably less than or equal to 7.5 parts by mass or less.
- the specific compound one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
- the curable resin composition of the present invention may further contain an onium salt. Further, in the present invention, the structure may be substantially free of onium salts.
- the term "substantially free” means that the content of the onium salt in the curable resin composition of the present invention is 5% by mass or less based on the total solid content of the curable resin composition, preferably 3 It means that it is 1% by mass or less, more preferably 1% by mass.
- 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 the anion may or may not be bonded via a covalent bond. .. That is, the onium salt may be an intermolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are different 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.
- ammonium cation As the ammonium cation, a quaternary ammonium cation is preferable.
- the ammonium cation is preferably a cation represented by the following 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.
- 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 group. 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 sulfate anion is preferable, and a carboxylic acid anion is more preferable because both the stability of the salt and the thermal decomposability 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 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 the substituent constant ⁇ m of Hammett shows a positive value.
- ⁇ m is a review article 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, and the onium salt is an anion.
- the onium salt is an anion.
- 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 specific precursor or the like is improved. Is more preferable.
- the above pKa includes Determination of Organic Strategies by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O., Nachod, F. See Nachod, FC; 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 have the same meaning as 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 a structure in 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.
- Each of R 8 to R 10 is preferably an alkyl group or an aryl group independently, 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 group.
- Examples thereof include a carbonyl group and an acyloxy group.
- 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 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 diallyl 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 group.
- 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 independently represent a hydrogen atom or a hydrocarbon group.
- Each of R 13 to R 16 is preferably an alkyl group or an aryl group independently, 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 group.
- 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 based on 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 kinds are used, the total amount is preferably in the above range.
- the curable resin composition of the present invention may further contain the above-mentioned other thermosetting agents. Further, in the present invention, a configuration that does not substantially contain other thermobase generators can be used.
- the term "substantially free” means that the content of the other thermosetting agent in the curable resin composition of the present invention is 5% by mass or less based on the total solid content of the curable resin composition. It means that it is preferably 3% by mass or less, and more preferably 1% by mass.
- 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 monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable.
- the single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring.
- a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.
- Rb 1 and Rb 2 are hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and alkenyl groups (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ⁇ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have 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.
- 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 even more 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), and 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 effects of the present invention are 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 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), aryl group (6 to 22 carbon atoms are preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7).
- Rb 17 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), 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 thermosetting agent 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 kinds are used, the total amount is preferably in the above range.
- the curable resin composition of the present invention contains an anion represented by the following formula (TBG-1) or the following formula (TBG-2) (hereinafter, also referred to as "specific anion") as a thermobase generator. It may be.
- the specific anion may form a salt structure with a cation such as an organic cation described later, or may be dissociated and exist in an anion state.
- a compound which is a salt of the specific anion and the organic cation described later, or a solution of the above compound is used. It may be prepared by mixing with other components contained in the composition such as a heterocyclic ring-containing polymer.
- R 11 and R 12 each independently represent a hydrogen atom or an organic group, and R 11 and R 12 may be bonded to form a ring structure.
- R 21 and R 22 each independently represent a hydrogen atom or an organic group, R 21 and R 22 may be bonded to form a ring structure, and * represents a bonding site with another structure.
- R 11 and R 12 are preferably hydrogen atoms or aliphatic hydrocarbon groups, respectively, and are preferably aliphatic hydrocarbon groups. More preferably, it is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 2 to 6 carbon atoms or 3 to 3 carbon atoms.
- the cyclic alkyl group of 8 is particularly preferable, and the isopropyl group or cyclohexyl group is most preferable.
- R 11 and R 12 may be combined to form a ring structure, and the ring structures formed include a pyrrolidine ring structure, an imidazolidine ring structure, a pyrazoledin ring structure, a piperidine ring structure, a piperazine ring structure, and morpholin.
- a nitrogen-containing aliphatic ring structure such as a ring structure, a pyrrol ring structure, an imidazole ring structure, a pyridine ring structure, a pyrazine ring structure, a pyrimidine ring structure, and a nitrogen-containing aromatic ring structure such as a pyridazine ring structure.
- At least one of the nitrogen atoms contained in the nitrogen-containing aliphatic ring structure or the nitrogen-containing aromatic ring structure is a nitrogen atom to which R 11 and R 12 described in the formula (TBG-1) are bonded. ..
- R 11 and R 12, or ring structure and R 11 and R 12 are formed by bonding, it may further have a substituent.
- a known substituent can be used as long as the effect of the present invention can be obtained, and examples thereof include an alkyl group, an aryl group, and a halogen atom.
- at least one of R 11 and R 12, or ring structure and R 11 and R 12 are formed by bonding may have a group having an ethylenically unsaturated bond as a substituent.
- Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acryloyl group, and the above formula. Examples thereof include the group represented by (III).
- R 21 and R 22 are synonymous with R 11 and R 12 in the formula (TBG-1), respectively, and the preferred embodiments are also the same.
- the molecular weight of the specific anion is preferably 150 to 2,000, more preferably 150 to 1,000, and even more preferably 160 to 800.
- Specific examples of the specific anion include, but are not limited to, the anion portion in the compounds represented by the formulas (BA-1) to (BA-22) described later.
- the curable resin composition of the present invention may contain a compound which is a salt of a specific anion and an organic cation.
- the compound which is a salt of the specific anion and the organic cation may be present as a salt of the specific anion and the organic cation in the curable resin composition, or may be dissociated into the specific anion and the organic cation.
- it may be a compound that exists as a salt of a specific anion and an organic cation when stored at 20 ° C. or the like, and dissociates the specific anion and the organic cation when heated at 180 ° C. or the like.
- the organic cation is not particularly limited, but is preferably a monovalent organic cation.
- the organic cation is preferably an ammonium cation, an iminium cation, or a phosphonium cation.
- organic cation examples include, but are not limited to, the anion moiety in the compounds represented by the formulas (BA-1) to (BA-22) described later.
- organic cation an ammonium cation, an iminium cation, or a phosphonium cation described later in the description of the onium salt can also be preferably used.
- Specific examples of the compound which is a salt of a specific anion and an organic cation include, but are not limited to, compounds represented by the following formulas (BA-1) to (BA-22).
- the content of the compound, which is a salt of the specific anion and the organic cation, is based on the total solid content of the curable resin composition from the viewpoint of improving the storage stability of the composition and the elongation at break of the obtained cured film. , 0.005 to 50% by mass is preferable.
- the lower limit is more preferably 0.05% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.
- the upper limit is more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less, from the viewpoint of corrosion resistance of a metal (for example, copper used for wiring or the like).
- the content of the compound which is a salt of the specific anion and the organic cation with respect to 100 parts by mass of the heterocyclic-containing polymer precursor is from the viewpoint of improving the storage stability of the composition and the breaking elongation rate of the obtained cured film. , 0.005 parts by mass or more, more preferably 0.06 parts by mass or more, further preferably 0.5 parts by mass or more, and further preferably 1 part by mass or more.
- the upper limit is preferably, for example, 20 parts by mass or less, more preferably 15 parts by mass or less, and 10 parts by mass. It is more preferably less than or equal to 7.5 parts by mass or less.
- the composition may be substantially free of a compound which is a salt of a specific anion and an organic cation.
- substantially free means that the content of the other thermosetting agent in the curable resin composition of the present invention is 5% by mass or less based on the total solid content of the curable resin composition. It means that it is preferably 3% by mass or less, and more preferably 1% by mass.
- the compound which is a salt of a specific anion and an organic cation one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
- the curable resin composition of the present invention preferably contains a photopolymerization initiator.
- 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 in the ultraviolet region to the visible region is preferable.
- it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
- 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.
- halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
- acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like.
- Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned.
- paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.
- ketone compound for example, the compound described in paragraph 0087 of JP2015-087611A is exemplified, and the content thereof is incorporated in the present specification.
- KayaCure DETX manufactured by Nippon Kayaku Co., Ltd.
- Nippon Kayaku Co., Ltd. is also preferably used.
- a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
- IRGACURE 184 (IRGACURE is a registered trademark)
- DAROCUR 1173 As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.
- aminoacetophenone-based initiator commercially available products IRGACURE 907, IRGACURE 369, IRGACURE 379 (trade name: all manufactured by BASF), Omnirad 907, Omnirad 369, and Omnirad 379 (all manufactured by IGM Resin). ) Can be used.
- the compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
- acylphosphine-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
- commercially available products such as IRGACURE-819, IRGACURE-TPO (trade name: all manufactured by BASF), Omnirad 819 and Omnirad TPO (all manufactured by IGM Resins) can be used.
- metallocene compound examples include IRGACURE-784 (manufactured by BASF).
- An oxime compound is more preferable as the photoradical polymerization initiator.
- the exposure latitude can be improved more effectively.
- the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
- the compound described in JP-A-2001-233842 the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.
- Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
- an oxime compound (oxime-based 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).
- the radical polymerization initiator 2) is also preferably used.
- TR-PBG-304 manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.
- Adeka Arkuru's NCI-831 and Adeka Arkuru's NCI-930 can also be used.
- DFI-091 manufactured by Daito Chemix Corp.
- an oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.
- Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.
- the photoradical polymerization initiator includes 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, and a triaryl.
- a trihalomethyltriazine compound Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.
- More 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
- -2-morpholino-aromatic ketones such as propanol-1, alkylanthraquinone, etc.
- benzoin ether compounds such as benzoin alkyl ether
- benzoin compounds such as benzoin and alkyl benzoin
- benzyl derivatives such as benzyl dimethyl ketal.
- a compound represented by the following formula (I) can also be used.
- R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like.
- R I01 is a group represented by formula (II), the same as R I00
- the groups, R I02 to R I04, are independently alkyls having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogens, respectively.
- R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
- the 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 curable resin 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 is preferably in the above range.
- the curable resin composition of the present invention may contain a thermal polymerization initiator as the polymerization initiator, and may particularly contain 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 heterocyclic polymer precursor can be allowed to proceed as well as the cyclization of the heterocyclic polymer precursor, so that higher heat resistance can be achieved.
- thermal radical polymerization initiator examples include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
- thermosetting polymerization initiator When the thermosetting polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. %, More preferably 5 to 15% by mass. Only one type of thermal radical polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal radical polymerization initiators are contained, the total is preferably in the above range.
- the curable resin composition of the present invention preferably further contains a polymerizable compound.
- a radically polymerizable compound can be used as the polymerizable compound.
- the radically polymerizable compound is a compound having a radically polymerizable group.
- examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
- the radically polymerizable group is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.
- the number of radically polymerizable groups contained in the radically polymerizable compound may be one or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, and preferably has three or more radically polymerizable groups. More preferred.
- the upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.
- the molecular weight of the radically polymerizable compound 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 radically polymerizable compound is preferably 100 or more.
- the curable resin composition of the present invention preferably contains at least one bifunctional or higher functional radical polymerizable compound containing two or more radical polymerizable groups, and is preferably a trifunctional or higher functional radical polymerizable compound. It is more preferable to contain at least one kind. Further, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound.
- the number of functional groups of a bifunctional or higher-functional polymerizable monomer means that the number of radically polymerizable groups in one molecule is two or more.
- the radically polymerizable compound examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and preferred examples thereof.
- an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group.
- a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
- an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amines or thiols, and a halogeno group.
- Substitution reactions of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
- 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.
- radically polymerizable compounds other than the above those described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like have a fluorene ring and have an ethylenically unsaturated bond. It is also possible to use a compound having two or more groups having the above, or a cardo resin.
- the compound described in Japanese Patent Application Laid-Open No. 10-062986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol is also (meth) acrylated. It can be used as a radically polymerizable compound.
- radically polymerizable compound examples include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku (commercially available)).
- SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
- SR-209 which is a bifunctional methacrylate having four ethyleneoxy chains.
- 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, 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 ( Nippon 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 Nikko Co., Ltd.), etc. Can be mentioned.
- Examples of the radically polymerizable compound include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765.
- Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
- radically polymerizable compound 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. It can also be used.
- the radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxy group or a phosphoric acid group.
- the radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
- a radically polymerizable compound having a group is more preferable.
- the aliphatic polyhydroxy compound in a radical polymerizable compound in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, is pentaerythritol or dipenta. It is a compound that is erythritol.
- 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 radically polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
- the acid value of the radically polymerizable compound is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizable property is good.
- the acid value is measured according to the description of JIS K 0070: 1992.
- a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the cured film.
- the monofunctional radically polymerizable compound include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth).
- Acrylate 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 polymerizable compound 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 curable resin composition of the present invention can further contain a polymerizable compound other than the radically polymerizable compound described above.
- a polymerizable compound other than the above-mentioned radically polymerizable compound include a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound.
- R 104 represents an organic group having a t-valence of 1 to 200 carbon atoms
- R 105 is a group represented by -OR 106 or -OCO-R 107.
- R 106 indicates a hydrogen atom or an organic group having 1 to 10 carbon atoms
- R 107 indicates an organic group having 1 to 10 carbon atoms.
- R 404 represents a divalent organic group having 1 to 200 carbon atoms
- R 405 represents a group represented by -OR 406 or -OCO-R 407
- R 406 is a hydrogen atom or carbon.
- R 407 indicates an organic group having 1 to 10 carbon atoms.
- u represents an integer of 3 to 8
- R 504 represents a u-valent organic group having 1 to 200 carbon atoms
- R 505 indicates a group represented by -OR 506 or -OCO-R 507.
- R 506 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
- R 507 represents an organic group having 1 to 10 carbon atoms.
- Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML.
- Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, and the like.
- HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), NIKALAC MX-280, Examples thereof include NIKALAC MX-270 and NIKALAC MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).
- the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
- the epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the 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; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidi).
- epoxy groups include, but are not limited to, epoxy group-containing silicones such as loxypropyl) siloxane.
- an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance.
- an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance.
- Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain polyethylene oxide groups.
- oxetane compound compound having an oxetanyl group
- 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 Preferred examples of the benzoxazine compound are BA type benzoxazine, Bm type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzo.
- Oxazine compounds can be mentioned. These may be used alone or in combination of two or more.
- the content 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 polymerizable compound 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 a solvent.
- a solvent a known solvent can be arbitrarily used.
- the solvent is preferably an organic solvent.
- the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
- esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone.
- alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )
- 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
- 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate
- Etc. eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate
- 2-alkyloxy-2-methylpropionate etc.
- Methyl acid and ethyl 2-alkyloxy-2-methylpropionate eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
- methyl pyruvate, ethyl pyruvate, pyruvin Propyl acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate and the like are preferred.
- ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol.
- Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
- ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferable.
- aromatic hydrocarbons for example, toluene, xylene, anisole, limonene and the like are preferable.
- sulfoxides for example, dimethyl sulfoxide is preferable.
- N-methyl-2-pyrrolidone N-ethyl-2-pyrrolidone
- N, N-dimethylacetamide N, N-dimethylformamide and the like are preferable.
- the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
- the mixed solvent to be mixed is preferable.
- the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
- the content of the solvent is preferably such that the total solid content concentration of the 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 solvent may contain only one type or two or more types. 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 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 migration inhibitor is not particularly limited, but heterocycles (pyrazole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
- triazole-based compounds such as 1,2,4-triazole and benzotriazole
- tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.
- an ion trap agent that traps anions such as halogen ions can also be used.
- Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656.
- the compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used.
- the migration inhibitor include the following compounds.
- the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the 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, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'.
- -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, Bis (4-hydroxy-3,5-ter
- the content of the polymerization inhibitor shall be 0.01 to 5% by mass with respect to the total solid content of the curable resin composition of the present invention. Is more preferable, 0.02 to 3% by mass is more preferable, and 0.05 to 2.5% by mass is further preferable.
- 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 adhesiveness improving agent include a silane coupling agent.
- silane coupling agent examples include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992.
- Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Further, it is also preferable to use the following compounds as the silane coupling agent.
- Et represents an ethyl group.
- the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used. ..
- the content of the metal 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. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are good.
- the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.
- the curable resin composition of the present invention can be used with various additives such as a thermoacid generator, a sensitizer such as N-phenyldiethanolamine, and a chain transfer agent, if necessary, as long as the effects of the present invention can be obtained.
- additives such as a thermoacid generator, a sensitizer such as N-phenyldiethanolamine, and a chain transfer agent, if necessary, as long as the effects of the present invention can be obtained.
- Surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, antiaggregating agents and the like can be blended.
- the total blending amount is preferably 3% by mass or less of the solid content of the 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 electron-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.
- the sensitizer include sensitizers such as N-phenyldiethanolamine.
- sensitizing dye As a sensitizer, you may use a sensitizing dye as a 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.
- 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. Only one type of surfactant may be used, or two or more types may be used. When there are two or more types of surfactant, the total is preferably in the above range.
- 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 with respect to 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 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.
- 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, still 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, it is preferable that the total of these metals is in the above range.
- a raw material having a low metal content is selected as 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.
- 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 bottle having a layered structure. 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 can be prepared by mixing each of the above components.
- the mixing method is not particularly limited, and a conventionally known method can be used.
- the filter pore diameter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
- the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
- the filter may be one that has been pre-cleaned with an organic solvent.
- a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times.
- circulation filtration When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
- impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
- adsorbent a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
- the 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 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.
- An embodiment in which the resin composition is a cured film is preferable.
- 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 the applicable field of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
- a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above may be patterned by etching. For these applications, for example, Science & Technology Co., Ltd.
- the cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially microelectronics.
- the method for producing a cured film of the present invention includes a film forming step of applying the 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
- Exposure Development step for developing the film
- Heating step for heating the developed film at 50 to 450 ° C. By heating in the 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.
- 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 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).
- the type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film transistor. There are no particular restrictions on magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, and plasma display panel (PDP) electrode plates. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material is more preferable. Further, as the base material, for example, a plate-shaped base material (board) is used.
- 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 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 used.
- the method, the inkjet method and the like are preferable.
- the spin coating method for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute.
- the transfer method the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention.
- the production method of the present invention may include a step of forming the film (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. As a result, particularly high exposure sensitivity can be obtained.
- the production method of the present invention may include a developing step of developing (developing the above film) the exposed film (curable resin composition layer). By performing the development, the unexposed portion (non-exposed portion) is removed.
- the developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.
- the developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
- alkaline development the case where an alkaline developer is used as the developer
- solvent development the case where a developer containing 50% by mass or more of an organic solvent is used as the developer.
- the developer preferably has an organic solvent content of 10% by mass or less based on the total mass of the developer.
- the content is more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably not containing an organic solvent.
- the developing solution in alkaline development is more preferably an aqueous solution having a pH of 10 to 14.
- Examples of the alkaline compound contained in the developing solution in alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicate. Examples include potassium silicate, ammonia or amine.
- amines examples include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, and tetramethylammonium hydroxide.
- TMAH tetraethylammonium hydroxide
- tetrabutylammonium hydroxide and the like can be mentioned.
- metal-free alkaline compounds are preferable, and amines are more preferable.
- the alkaline compound may be only one kind or two or more kinds. When there are two or more alkaline compounds, the total is preferably in the above range.
- the developer used in solvent development preferably has 60% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and 90% by mass or more of an organic solvent with respect to the total mass of the developer. It is more preferably a solvent. Further, the developing solution may be 100% by mass of an organic solvent with respect to the total mass of the developing solution.
- 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 includes, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone.
- alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl propionate ethoxyacetate, etc.)
- alkyl esters of 3-alkyloxypropionate eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
- 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-
- Ke Tons include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc.
- Dimethyl sulfoxide is preferably mentioned as the sulfoxides.
- cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.
- the development time is preferably 10 seconds to 5 minutes.
- the temperature of the developing solution at the time of development is not particularly specified, but is usually 20 to 40 ° C.
- the rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with a solvent contained in the curable resin composition.
- the rinsing time is preferably 5 seconds to 1 minute.
- the production method of the present invention preferably includes a step (heating step) of heating the developed film 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 heating step for example, the above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the heterocyclic polymer precursor proceeds.
- the curable resin composition of the present invention may contain a radically polymerizable compound other than the heterocyclic polymer precursor, but may also cure a radically polymerizable compound other than the unreacted heterocyclic polymer precursor. 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 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 heterocyclic polymer precursor between the layers are undergoing a cross-linking reaction at this temperature.
- Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed.
- the heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547.
- the pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
- the pretreatment may be performed in two or more steps.
- the pretreatment step 1 may be performed in the range of 100 to 150 ° C.
- the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
- cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
- the heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the heterocyclic polymer precursor.
- the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
- the production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (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, copper and aluminum are more preferable, and copper is preferable. More preferred.
- the method for forming the metal layer is not particularly limited, and an existing method can be applied.
- the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used.
- photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
- the thickness of the metal layer is preferably 0.1 to 50 ⁇ m, more preferably 1 to 10 ⁇ m 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 steps of (d) are collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step, and the like as appropriate.
- the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step.
- An example of the surface activation treatment is plasma treatment.
- the laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
- the resin layer is 3 or more and 7 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and 3 or more and 5 or less are more preferable.
- a cured film (resin layer) of the curable resin composition so as to cover the metal layer after the metal layer is provided.
- Examples thereof include an embodiment in which the steps, (b) exposure steps, (c) development steps, and (e) metal layer forming steps are repeated in this order, and (d) heating steps are collectively provided at the end or in the middle.
- the present invention also discloses a semiconductor device containing the cured film or laminate of the present invention.
- 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 polyimide precursor resin was then precipitated in 4 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes.
- the polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 3 days.
- the weight average molecular weight of the obtained polyimide precursor A-2 was 23,500, and the number average molecular weight was 8,800.
- the polyamide-imide precursor resin was then precipitated in 4 liters of water and the water-polyamideimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes.
- the polyamide-imide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyamide-imide precursor resin was dried under reduced pressure at 45 ° C. for 3 days.
- the weight average molecular weight of the obtained polyamide-imide precursor was 23,800, and the number average molecular weight was 9,900.
- the polybenzoxazole precursor resin was obtained by filtration, stirred again in 6 liters of water for 30 minutes and filtered again. Then, the obtained polybenzoxazole precursor resin was dried under reduced pressure at 45 ° C. for 3 days.
- the obtained polybenzoxazole precursor A-4 had a weight average molecular weight of 21,500 and a number average molecular weight of 9,500.
- ⁇ Synthesis example 5> [Synthesis of polyimide precursor (A-5: polyimide precursor having radical polymerizable group) from 4,4'-oxydiphthaldioic anhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate] 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of ⁇ -butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine with stirring at room temperature. After the exotherm by the reaction was completed, the mixture was allowed to cool to room temperature and allowed to stand for another 16 hours.
- ODPA 4,4'-oxydiphthalic dianhydride
- HEMA 2-hydroxyethyl methacrylate
- a reaction mixture was obtained by adding 79.1 g of pyridine
- 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 collected by filtration 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 the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polymer A-5.
- the weight average molecular weight (Mw) of this polymer A-5 was measured and found to be 20,000.
- Tetrahydrofuran in the filtrate was distilled off, dissolved in 300 mL of ethyl acetate, and transferred to a separating funnel. It was then washed twice with 100 mL of water and twice with 150 mL of saturated brine and dried over sodium sulfate. This was transferred to a 1-neck flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 33 g of BG-1. The fact that it was BG-1 was confirmed from 1 1 H-NMR spectrum. 1 1 H-NMR data is shown below.
- Tetrahydrofuran in the filtrate was distilled off, dissolved in 300 mL of ethyl acetate, and transferred to a separating funnel. It was then washed twice with 100 mL of water and twice with 150 mL of saturated brine and dried over sodium sulfate. This was transferred to a 1-neck flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 31 g of BG-2. The fact that it was BG-2 was confirmed from 1 1 H-NMR spectrum. 1 1 H-NMR data is shown below.
- Tetrahydrofuran in the filtrate was removed by an evaporator, 40 mL of BG-3 was dissolved in dehydrated tetrahydrofuran, and the mixture was allowed to stand at ⁇ 5 ° C. for 1 day. The generated crystals were filtered, washed with 30 mL of tetrahydrofuran, and vacuum dried at 25 ° C. for 3 hours to obtain 15 g of BG-3. The fact that it was BG-3 was confirmed from 1 1 H-NMR spectrum. 1 1 H-NMR data is shown below.
- the filtrate was transferred to a separatory funnel, washed twice with 50 mL of water and twice with 150 mL of saturated brine, and dried over sodium sulfate. This was transferred to a 1-neck flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 12 g of BG-4.
- Examples and Comparative Examples> the components shown in Table 1 or Table 2 below were mixed to obtain each curable resin composition. Further, in each comparative example, the components shown in Table 2 below were mixed to obtain each comparative composition. Specifically, the content of the component shown in Table 1 or Table 2 was the amount shown in "Mass part" of Table 1 or Table 2.
- 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 Table 1 or Table 2, the description of "-" indicates that the composition does not contain the corresponding component.
- Heterocycle-containing polymer precursor] -A-1 to A-6 A-1 to A-6 synthesized above In Example 25, 16.9 parts by mass of A-5 and 16.9 parts by mass of A-6 were used.
- BG-1 to BG-18 BG-1 to BG-18 synthesized above -B-1 to B-2: Compounds having the following structures. None of B-1 to B-2 has a structure represented by the formula (1-1) and does not correspond to a specific compound.
- ⁇ solvent ⁇ -DMSO dimethyl sulfoxide-GBL: ⁇ -butyrolactone-NMP: N-methylpyrrolidone
- [Metal adhesion improver] -G-1 The following compound-G-2: The following compound-G-3: The following compound-G-4: The following compound Et represents an ethyl group.
- thermobase generators -I-1 to I-3: Compounds having the following structure
- 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 uniform curable resin composition layer having a thickness of about 15 ⁇ m on the silicon wafer.
- the entire surface of the obtained curable resin composition layer was exposed to i-rays with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).
- the curable resin composition layer (resin layer) after the above exposure is heated at a heating rate of 10 ° C./min under a nitrogen atmosphere, and is displayed in the “Curing temperature (° C.)” column of Table 1 or Table 2. After reaching the stated temperature, it was heated for 3 hours.
- the cured resin layer (cured film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured film was peeled off from the silicon wafer. The peeled cured film was punched out using a punching machine to prepare a test piece having a sample width of 3 mm and a sample length of 30 mm.
- the obtained test piece was subjected to a film in accordance with JIS-K6251 using a tensile tester (Tencilon) at a crosshead speed of 300 mm / min and in an environment of 25 ° C. and 65% RH (relative humidity).
- the elongation at break in the longitudinal direction was measured.
- the evaluation was carried out 5 times each, and the arithmetic mean value of the elongation rate (break elongation rate) when the film was broken was used as an index value.
- the above index values were evaluated according to the following evaluation criteria, and the evaluation results were described in the “Film strength” column of Table 1 or Table 2. It can be said that the larger the index value is, the better the film strength (break elongation) of the obtained cured film is.
- 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 layer was formed by applying it on a silicon wafer by a spin coating method using the same rotation speed as in the case of.
- 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 listed in the "Storage stability" column of Table 1 or Table 2. 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 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 form a curable resin composition layer having a uniform thickness of 15 ⁇ m on the silicon wafer.
- the curable resin composition layer on the silicon wafer was i-line-exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed curable resin composition layer (resin layer) was subjected to i-line exposure.
- a cured layer (resin layer) of a curable resin composition layer was obtained by heating in a nitrogen atmosphere at a heating rate of 10 ° C./min and heating at the temperatures shown in Table 1 or 2 for 3 hours. ..
- the obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
- Chemical solution A mixture of dimethyl sulfoxide (DMSO) and a 25 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 90:10 (mass ratio)
- DMSO dimethyl sulfoxide
- TMAH tetramethylammonium hydroxide
- Evaluation conditions The resin layer is immersed in the above chemical solution at 75 ° C. for 15 minutes before and after. The film thicknesses were compared and the dissolution rate (nm / min) was calculated.
- 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 evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the "Chemical resistance" column of Table 1 or Table 2. It can be said that the smaller the value of the dissolution rate, the better the chemical resistance of the obtained cured film (resin layer).
- the heterocyclic polymer precursor and the curable resin composition containing the specific compound according to the present invention are excellent in the film strength of the cured film and the storage stability of the composition.
- the curable resin compositions according to Comparative Examples 1 to 5 do not contain a specific compound. It can be seen that the curable resin compositions according to Comparative Examples 1 to 5 are inferior to at least one of the film strength of the cured film and the storage stability of the composition.
- 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). Exposure was performed at a wavelength of 365 nm via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m). After exposure, it was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a layer pattern.
- NSR1505 i6 a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m
- 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
<1> ポリイミド前駆体、ポリアミドイミド前駆体、及び、ポリベンゾオキサゾール前駆体よりなる群から選ばれた少なくとも1種の樹脂、並びに、
下記式(1-1)で表される構造を有する化合物を含む
硬化性樹脂組成物。
<2> 上記式(1-1)におけるArが5員環構造である、<1>に記載の硬化性樹脂組成物。
<3> 上記式(1-1)で表される構造が、下記式(1-2)で表される構造である、<1>又は<2>に記載の硬化性樹脂組成物。
<4> 上記式(1-1)で表される構造を有する化合物が、下記式(1-3)で表される化合物である、<1>~<3>のいずれか1つに記載の硬化性樹脂組成物。
<5> 上記X1が芳香族炭化水素環構造を含む、<4>に記載の硬化性樹脂組成物。
<6> 上記式(1-1)で表される構造を有する化合物の分子量が、90~500である、<1>~<5>のいずれか1つに記載の硬化性樹脂組成物。
<7> 上記式(1-1)で表される構造を有する化合物が、熱塩基発生剤である、<1>~<6>のいずれか1つに記載の硬化性樹脂組成物。
<8> 光重合開始剤、及び、重合性化合物を更に含む、<1>~<7>のいずれか1つに記載の硬化性樹脂組成物。
<9> 再配線層用層間絶縁膜の形成に用いられる、<1>~<8>のいずれか1つに記載の硬化性樹脂組成物。
<10> <1>~<9>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。
<11> <10>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。
<12> <1>~<9>のいずれか1つに記載の硬化性樹脂組成物を基材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。
<13> 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、<12>に記載の硬化膜の製造方法。
<14> 上記膜を50~450℃で加熱する加熱工程を含む、<12>又は<13>に記載の硬化膜の製造方法。
<15> <10>に記載の硬化膜又は<11>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 a polyimide precursor, a polyamide-imide precursor, and a polybenzoxazole precursor, and
A curable resin composition containing a compound having a structure represented by the following formula (1-1).
<2> The curable resin composition according to <1>, wherein Ar in the above formula (1-1) has a 5-membered ring structure.
<3> The curable resin composition according to <1> or <2>, wherein the structure represented by the above formula (1-1) is a structure represented by the following formula (1-2).
<4> The compound according to any one of <1> to <3>, wherein the compound having the structure represented by the above formula (1-1) is a compound represented by the following formula (1-3). Curable resin composition.
<5> The curable resin composition according to <4>, wherein X 1 contains an aromatic hydrocarbon ring structure.
<6> The curable resin composition according to any one of <1> to <5>, wherein the compound having the structure represented by the above formula (1-1) has a molecular weight of 90 to 500.
<7> The curable resin composition according to any one of <1> to <6>, wherein the compound having the structure represented by the above formula (1-1) is a thermosetting agent.
<8> The curable resin composition according to any one of <1> to <7>, further comprising a photopolymerization initiator and a polymerizable compound.
<9> The curable resin composition according to any one of <1> to <8>, which is used for forming an interlayer insulating film for a rewiring layer.
<10> A cured film obtained by curing the curable resin composition according to any one of <1> to <9>.
<11> A laminate containing two or more layers of the cured film according to <10> and containing a metal layer between any of the cured films.
<12> 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 <9> to a substrate to form a film.
<13> The method for producing a cured film according to <12>, which comprises an exposure step of exposing the film and a developing step of developing the film.
<14> The method for producing a cured film according to <12> or <13>, which comprises a heating step of heating the film at 50 to 450 ° C.
<15> A semiconductor device comprising the cured film according to <10> or the laminate according to <11>.
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)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 using 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 electron beams and ion beams. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or , And "(meth) acryloyl" means both "acryloyl" and "methacrylic", 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 above or below 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. and the atmospheric pressure is 101,325 Pa (1 atm).
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は、ポリイミド前駆体、ポリアミドイミド前駆体、及び、ポリベンゾオキサゾール前駆体よりなる群から選ばれた少なくとも1種の樹脂、並びに、下記式(1-1)で表される構造を有する化合物を含む。
また、本発明の硬化性樹脂組成物は、光重合開始剤、及び、重合性化合物を更に含むことが好ましい。
The curable resin composition of the present invention is represented by at least one resin selected from the group consisting of a polyimide precursor, a polyamide-imide precursor, and a polybenzoxazole precursor, and the following formula (1-1). Includes compounds that have the structure to be.
Further, the curable resin composition of the present invention preferably further contains a photopolymerization initiator and a polymerizable compound.
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。 The curable resin composition of the present invention is excellent in storage stability of the composition and the film strength of the obtained cured film.
The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
本発明の硬化性樹脂組成物は、式(1-1)で表される構造を有する化合物を含む。低温における保管時においては、上記化合物が、硬化性樹脂組成物中のアミン化合物をトラップすることにより、組成物の保存安定性が向上すると考えられる。
また、加熱時等のポリマー前駆体の硬化時においては、上記化合物から、例えば、トラップしたアミン化合物、塩基性芳香族化合物等の塩基が発生することにより、複素環含有ポリマー前駆体の環化率が高くなり、得られる硬化膜の膜強度が向上すると考えられる。
また、ポリマー前駆体を含む硬化性樹脂組成物を硬化してなる硬化膜の形成においては、例えば、硬化膜上に更に硬化性樹脂組成物を適用、硬化して積層体を作製する場合等に、先に形成された硬化膜が現像液又は他の組成物に接する場合がある。
そのため、硬化性樹脂組成物において、例えば、硬化膜の現像液への耐性又は他の組成物との接触による硬化膜の溶解の抑制等の観点から、得られる硬化膜の耐薬品性に優れる硬化性樹脂組成物の提供が望まれている。
本発明の硬化性樹脂組成物においては、上述の機序により硬化膜における複素環含有ポリマー前駆体の環化率が高くなるため、硬化膜の耐薬品性にも優れやすいと考えられる。 Conventionally, a curable resin composition containing a polymer precursor has been used for applications such as applying it to a substrate or the like and then heating or the like to cyclize the precursor to obtain a cured film containing a polyimide resin or the like. I came.
The curable resin composition of the present invention contains a compound having a structure represented by the formula (1-1). It is considered that the above compound traps the amine compound in the curable resin composition during storage at a low temperature, thereby improving the storage stability of the composition.
Further, during curing of the polymer precursor such as during heating, the cyclization rate of the heterocyclic polymer precursor is generated by generating a base such as a trapped amine compound or a basic aromatic compound from the above compound. Is considered to increase, and the film strength of the obtained cured film is improved.
Further, in the formation of a cured film formed by curing a curable resin composition containing a polymer precursor, for example, when a curable resin composition is further applied on the cured film and cured to prepare a laminate. , The cured film formed earlier may come into contact with the developer or other composition.
Therefore, in the curable resin composition, for example, from the viewpoint of resistance of the cured film to a developing solution or suppression of dissolution of the cured film due to contact with other compositions, the obtained cured film is cured with excellent chemical resistance. It is desired to provide a sex resin composition.
In the curable resin composition of the present invention, since the cyclization rate of the heterocyclic polymer precursor in the cured film is increased by the above mechanism, it is considered that the cured film is likely to have excellent chemical resistance.
以下、本発明の硬化性樹脂組成物に含まれる成分について詳細に説明する。 Here, Patent Document 1 does not describe or suggest a curable resin composition containing a compound having a structure represented by the formula (1-1).
Hereinafter, the components contained in 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は、複素環含有ポリマー前駆体を含む。
本発明の硬化性樹脂組成物は、上記複素環含有ポリマー前駆体として、ポリイミド前駆体、ポリアミドイミド前駆体及びポリベンゾオキサゾール前駆体よりなる群から選ばれた少なくとも1種の前駆体を含み、ポリイミド前駆体を含むことが好ましい。 <Heterocycle-containing polymer precursor>
The curable resin composition of the present invention contains a heterocyclic polymer precursor.
The curable resin composition of the present invention contains at least one precursor selected from the group consisting of a polyimide precursor, a polyamide-imide precursor and a polybenzoxazole precursor as the heterocycle-containing polymer precursor, and is a polyimide. It preferably contains a precursor.
得られる硬化膜の膜強度の観点からは、ポリイミド前駆体又はポリアミドイミド前駆体は、下記式(1)で表される繰返し単位を有することが好ましい。
From the viewpoint of the film strength of the obtained cured film, the polyimide precursor or the polyamide-imide precursor preferably has a repeating unit represented by the following formula (1).
式(1)におけるA1及びA2は、それぞれ独立に、酸素原子又は-NH-を表し、酸素原子が好ましい。 -A 1 and A 2-
A 1 and A 2 in the formula (1) independently represent an oxygen atom or -NH-, and an oxygen atom is preferable.
式(1)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、直鎖状又は分岐鎖状の脂肪族基、環状の脂肪族基、及び芳香族基、複素芳香族基、又はこれらを2以上組み合わせた基が例示され、炭素数2~20の直鎖の脂肪族基、炭素数3~20の分岐の脂肪族基、炭素数3~20の環状の脂肪族基、炭素数6~20の芳香族基、又は、これらを2以上組み合わせた基が好ましく、炭素数6~20の芳香族基がより好ましい。 -R 111-
R 111 in the formula (1) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are combined, and the number of carbon atoms is exemplified. A linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or 2 of these. The group combined as described above is preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.
式(1)におけるR115は、4価の有機基を表す。4価の有機基としては、芳香環を含む4価の有機基が好ましく、下記式(5)又は式(6)で表される基がより好ましい。 -R 115-
R 115 in the formula (1) 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.
式(1)における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。R113及びR114の少なくとも一方がラジカル重合性基を含むことが好ましく、両方がラジカル重合性基を含むことがより好ましい。ラジカル重合性基としては、ラジカルの作用により、架橋反応することが可能な基であって、好ましい例として、エチレン性不飽和結合を有する基が挙げられる。 -R 113 and R 114-
R 113 and R 114 in the formula (1) independently represent a hydrogen atom or a monovalent organic group. At least one of R 113 and R 114 preferably contains a radically polymerizable group, and more preferably both contain a radically polymerizable group. Examples of the radically polymerizable group include a group capable of a cross-linking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond.
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-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-がより好ましい。
特に好ましくは、R200がメチル基で、R201がエチレン基である。
式(III)中、*は他の構造との結合部位を表す。
本発明におけるポリイミド前駆体又はポリアミドイミド前駆体の好ましい実施形態として、R113又はR114の1価の有機基として、1、2又は3つの、好ましくは1つの酸基を有する、脂肪族基、芳香族基及びアリールアルキル基などが挙げられる。具体的には、酸基を有する炭素数6~20の芳香族基、酸基を有する炭素数7~25のアリールアルキル基が挙げられる。より具体的には、酸基を有するフェニル基及び酸基を有するベンジル基が挙げられる。酸基は、ヒドロキシ基が好ましい。すなわち、R113又はR114はヒドロキシ基を有する基であることが好ましい。
R113又はR114が表す1価の有機基としては、現像液の溶解度を向上させる置換基が好ましく用いられる。 In formula (III), R 201 is an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom). ~ 12 is preferable, 1 to 6 is more preferable, 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, 1 to 6 is more preferable, and 1 to 3 is particularly preferable). The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene 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-, and more preferably an ethylene group, a propylene group, a trimethylene group, and -CH 2 CH (OH) CH 2- .
Particularly preferably, R 200 is a methyl group and R 201 is an ethylene group.
In formula (III), * represents a binding site with another structure.
A preferred embodiment of the polyimide or polyamideimide precursor in the present invention is an aliphatic group having 1, 2 or 3 or preferably 1 acid group as the monovalent organic group of R 113 or R 114 . Examples include aromatic groups and arylalkyl groups. Specific examples thereof include an aromatic group having an acid group having 6 to 20 carbon atoms and an arylalkyl group having an acid group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is preferably a hydroxy group. That is, R 113 or R 114 is preferably a group having a hydroxy group.
As the monovalent organic group represented by R 113 or R 114, a substituent that improves the solubility of the developing solution is preferably used.
複素環含有ポリマー前駆体がポリアミドイミド前駆体である場合、ポリアミドイミド前駆体は、下記式(PAI-1)で表される繰返し単位を更に含んでもよい。
When the heterocyclic-containing polymer precursor is a polyamide-imide precursor, the polyamide-imide precursor may further contain a repeating unit represented by the following formula (PAI-1).
式(PAI-1)中、R116は、直鎖状又は分岐鎖状の脂肪族基、環状の脂肪族基、及び芳香族基、複素芳香族基、又は単結合若しくは連結基によりこれらを2以上連結した基が例示され、炭素数2~20の直鎖の脂肪族基、炭素数3~20の分岐の脂肪族基、炭素数3~20の環状の脂肪族基、炭素数6~20の芳香族基、又は、単結合若しくは連結基によりこれらを2以上組み合わせた基が好ましく、炭素数6~20の芳香族基、又は、単結合若しくは連結基により炭素数6~20の芳香族基を2以上組み合わせた基がより好ましい。
上記連結基としては、-O-、-S-、-C(=O)-、-S(=O)2-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基が好ましく、-O-、-S-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基がより好ましい。
上記アルキレン基としては、炭素数1~20のアルキレン基が好ましく、炭素数1~10のアルキレン基がより好ましく、炭素数1~4のアルキレン基が更に好ましい。
上記ハロゲン化アルキレン基としては、炭素数1~20のハロゲン化アルキレン基が好ましく、炭素数1~10のハロゲン化アルキレン基がより好ましく、炭素数1~4のハロゲン化アルキレン基がより好ましい。また、上記ハロゲン化アルキレン基におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、フッ素原子が好ましい。上記ハロゲン化アルキレン基は、水素原子を有していても、水素原子の全てがハロゲン原子で置換されていてもよいが、水素原子の全てがハロゲン原子で置換されていることが好ましい。好ましいハロゲン化アルキレン基の例としては、(ジトリフルオロメチル)メチレン基等が挙げられる。
上記アリーレン基としては、フェニレン基又はナフチレン基が好ましく、フェニレン基がより好ましく、1,3-フェニレン基又は1,4-フェニレン基が更に好ましい。 In formula (PAI-1), R 116 represents a divalent organic group and R 111 represents a divalent organic group.
In formula (PAI-1), R 116 is composed of a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a single bond or a linking group. Examples of the above-mentioned linked groups include a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. The aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group. A group in which two or more of the above are combined is more preferable.
The linking group includes -O-, -S-, -C (= O)-, -S (= O) 2- , an alkylene group, a halogenated alkylene group, an arylene group, or a link in which two or more of these are bonded. The group is preferable, and —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
As the alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
As the halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom. Examples of preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
As the arylene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
本発明において、カルボキシ基を2つ有する化合物をジカルボン酸化合物、ハロゲン化されたカルボキシ基を2つ有する化合物をジカルボン酸ジハライド化合物という。
ジカルボン酸ジハライド化合物におけるカルボキシ基は、ハロゲン化されていればよいが、例えば、塩素化されていることが好ましい。すなわち、ジカルボン酸ジハライド化合物は、ジカルボン酸ジクロリド化合物であることが好ましい。
ポリアミドイミド前駆体の製造に用いられるハロゲン化されていてもよいジカルボン酸化合物又はジカルボン酸ジハライド化合物としては、直鎖状又は分岐鎖状の脂肪族、環状の脂肪族又は芳香族ジカルボン酸化合物又はジカルボン酸ジハライド化合物などが挙げられる。
これらのジカルボン酸化合物又はジカルボン酸ジハライド化合物は、1種のみ用いてもよいし、2種以上用いてもよい。 Further, R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
In the present invention, a compound having two carboxy groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound.
The carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
Examples of the halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids. Examples include aciddihalide compounds.
Only one kind or two or more kinds of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used.
芳香族基の例としては、上述のAR-1~AR-10等が挙げられる。 Specifically, the dicarboxylic acid compound or the dicarboxylic acid dihalide compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic fat having 3 to 20 carbon atoms. A dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group group, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms is preferable. Alternatively, a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferable.
Examples of aromatic groups include the above-mentioned AR-1 to AR-10.
ジカルボン酸ジハライド化合物の具体例としては、上記ジカルボン酸化合物の具体例における2つのカルボキシ基をハロゲン化した構造の化合物が挙げられる。 Specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-. Didimethylsuccinic 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, octafluoroadipic acid, 3-methyladipic acid, pimelliic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, Dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecane Diacid, nonadecandioic acid, eikosandioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosandioic acid, heptacosanedioic acid, octacosanedioic acid, nonakosandioic acid, triacanthani Acid, Hentria Contanedioic Acid, DotriaContandioic Acid, Diglycolic Acid, Phthalic Acid, Isophthalic Acid, Telephthalic Acid, 4,4'-biphenylcarboxylic Acid, 4,4'-biphenylcarboxylic Acid, 4,4'- Examples thereof include dicarboxydiphenyl ether and benzophenone-4,4'-dicarboxylic acid.
Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxy groups are halogenated in the specific examples of the dicarboxylic acid compound.
上記連結基としては、-O-、-S-、-C(=O)-、-S(=O)2-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基が好ましく、-O-、-S-、アルキレン基、ハロゲン化アルキレン基、アリーレン基、又はこれらを2以上結合した連結基がより好ましい。
上記アルキレン基としては、炭素数1~20のアルキレン基が好ましく、炭素数1~10のアルキレン基がより好ましく、炭素数1~4のアルキレン基が更に好ましい。
上記ハロゲン化アルキレン基としては、炭素数1~20のハロゲン化アルキレン基が好ましく、炭素数1~10のハロゲン化アルキレン基がより好ましく、炭素数1~4のハロゲン化アルキレン基がより好ましい。また、上記ハロゲン化アルキレン基におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、フッ素原子が好ましい。上記ハロゲン化アルキレン基は、水素原子を有していても、水素原子の全てがハロゲン原子で置換されていてもよいが、水素原子の全てがハロゲン原子で置換されていることが好ましい。好ましいハロゲン化アルキレン基の例としては、(ジトリフルオロメチル)メチレン基等が挙げられる。
上記アリーレン基としては、フェニレン基又はナフチレン基が好ましく、フェニレン基がより好ましく、1,3-フェニレン基又は1,4-フェニレン基が更に好ましい。 In formula (PAI-2), R 117 is composed of linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, heteroaromatic groups, or single-bonded or linked groups. Examples of the above-mentioned linked groups include a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. The aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable. A group in which two or more of the above are combined is more preferable.
The linking group includes -O-, -S-, -C (= O)-, -S (= O) 2- , an alkylene group, a halogenated alkylene group, an arylene group, or a link in which two or more of these are bonded. The group is preferable, and —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
As the alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
As the halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom. Examples of preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
As the arylene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
本発明において、カルボキシ基を3つ有する化合物をトリカルボン酸化合物という。
上記トリカルボン酸化合物の3つのカルボキシ基のうち2つのカルボキシ基は酸無水物化されていてもよい。
ポリアミドイミド前駆体の製造に用いられるハロゲン化されていてもよいトリカルボン酸化合物としては、分岐鎖状の脂肪族、環状の脂肪族又は芳香族のトリカルボン酸化合物などが挙げられる。
これらのトリカルボン酸化合物は、1種のみ用いてもよいし、2種以上用いてもよい。 Further, R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. Chlorination is preferable as the halogenation.
In the present invention, a compound having three carboxy groups is referred to as a tricarboxylic acid compound.
Of the three carboxy groups of the tricarboxylic acid compound, two carboxy groups may be acid anhydrideized.
Examples of the halogenated tricarboxylic acid compound used in the production of the polyamide-imide precursor include branched chain aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds.
Only one kind of these tricarboxylic acid compounds may be used, or two or more kinds may be used.
芳香族基の例としては、上述のAR-1~AR-10等が挙げられる。 Specifically, the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a carbon number of carbon atoms. A tricarboxylic acid compound containing 6 to 20 aromatic groups or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or carbon by a single bond or a linking group is preferable. A tricarboxylic acid compound containing a group in which two or more aromatic groups of several 6 to 20 are combined is more preferable.
Examples of aromatic groups include the above-mentioned AR-1 to AR-10.
これらの化合物は、2つのカルボキシ基が無水物化した化合物(例えば、トリメリット酸無水物)であってもよいし、少なくとも1つのカルボキシ基がハロゲン化した化合物(例えば、無水トリメリット酸クロリド)であってもよい。 Specific examples of the tricarboxylic acid compound include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid. (Or phthalic acid anhydride) and benzoic acid are single-bonded, with -O-, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- or phenylene group. Examples thereof include linked compounds.
These compounds may be compounds in which two carboxy groups are anhydrated (eg, trimellitic acid anhydride) or compounds in which at least one carboxy group is halogenated (eg, trimellitic acid chloride). There may be.
本発明におけるポリアミドイミド前駆体の一実施形態として、全繰返し単位に対し、式(1)で表される繰返し単位、式(PAI-1)で表される繰返し単位、及び、式(PAI-2)で表される繰返し単位の合計含有量が50モル%以上、更には70モル%以上、特には90モル%以上であるポリアミドイミド前駆体が例示される。上限としては100モル%以下が実際的である。 As one embodiment of the polyimide precursor in the present invention, 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units are the repeating units represented by the formula (1). Is exemplified. As an upper limit, 100 mol% or less is practical.
As one embodiment of the polyamide-imide precursor in the present invention, for all the repeating units, the repeating unit represented by the formula (1), the repeating unit represented by the formula (PAI-1), and the formula (PAI-2). ), The total content of the repeating unit is 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more, and the polyamide-imide precursor is exemplified. As an upper limit, 100 mol% or less is practical.
本明細書において、分子量の分散度とは、重量平均分子量を数平均分子量により除した値(重量平均分子量/数平均分子量)をいう。 The degree of dispersion of the molecular weight of the polyimide precursor or the polyamide-imide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
In the present specification, the degree of molecular weight dispersion means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).
ポリベンゾオキサゾール前駆体は、下記式(2)で表される繰返し単位を含むことが好ましい。
The polybenzoxazole precursor preferably contains a repeating unit represented by the following formula (2).
式(2)中、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(炭素数1~24が好ましく、1~12がより好ましく、1~6が特に好ましい)及び芳香族基(炭素数6~22が好ましく、6~14がより好ましく、6~12が特に好ましい)の少なくとも一方を含む基が好ましい。R121を構成する芳香族基としては、上記式(1)のR111の例が挙げられる。上記脂肪族基としては、直鎖の脂肪族基が好ましい。R121は、4,4’-オキシジベンゾイルクロリドに由来することが好ましい。 -R 121-
In formula (2), R 121 represents a divalent organic group. The divalent organic group includes an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, 6 to 14 carbon atoms). Is more preferable, and 6 to 12 is particularly preferable). Examples of the aromatic group constituting R 121 include R 111 of the above formula (1). As the aliphatic group, a linear aliphatic group is preferable. R 121 is preferably derived from 4,4'-oxydibenzoyl chloride.
式(2)中、R122は、4価の有機基を表す。4価の有機基としては、上記式(1)におけるR115と同義であり、好ましい範囲も同様である。R122は、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に由来することが好ましい。 -R 122-
In formula (2), R 122 represents a tetravalent organic group. The tetravalent organic group has the same meaning as R 115 in the above formula (1), and the preferable range is also the same. R 122 is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
R123及びR124は、それぞれ独立に、水素原子又は1価の有機基を表し、上記式(1)におけるR113及びR114と同義であり、好ましい範囲も同様である。 -R 123 and R 124-
R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R 113 and R 114 in the above formula (1), and the preferable range is also the same.
硬化性樹脂組成物を、後述する溶剤現像に用いる場合、複素環含有ポリマー前駆体の酸価は、1mmol/g以下であることが好ましく、0.5mmol/g以下であることがより好ましく、0.3mmol/g以下であることが更に好ましい。上記酸価の下限は特に限定されず、0mmol/g以上であればよい。
硬化性樹脂組成物を、後述するアルカリ現像に用いる場合、複素環含有ポリマー前駆体の酸価は、1~8mmol/gであることが好ましく、1.5~6mmol/gであることがより好ましく、2~5mmol/gであることが更に好ましい。
本発明において、複素環含有ポリマー前駆体の酸価とは、複素環含有ポリマー前駆体1gに含まれる酸基の量(mmol)をいう。
上記酸基とは、pH12以上のアルカリ(例えば水酸化ナトリウム)により、中和される基をいう。また、上記酸基は、pKaが10以下である基であることが好ましい。
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。 -Acid value-
When the curable resin composition is used for solvent development described later, the acid value of the heterocyclic polymer precursor is preferably 1 mmol / g or less, more preferably 0.5 mmol / g or less, and 0. More preferably, it is 3 mmol / g or less. The lower limit of the acid value is not particularly limited, and may be 0 mmol / g or more.
When the curable resin composition is used for alkaline development described later, the acid value of the heterocyclic polymer precursor is preferably 1 to 8 mmol / g, more preferably 1.5 to 6 mmol / g. It is more preferably 2 to 5 mmol / g.
In the present invention, the acid value of the heterocyclic polymer precursor refers to the amount (mmol) of acid groups contained in 1 g of the heterocyclic polymer precursor.
The acid group refers to a group that is neutralized by an alkali having a pH of 12 or higher (for example, sodium hydroxide). Further, the acid group is preferably a group having a pKa of 10 or less.
The acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
本発明の硬化性樹脂組成物は、式(1-1)で表される構造を有する化合物(以下、「特定化合物」ともいう。)を含む。 <Compound having a structure represented by the formula (1-1)>
The curable resin composition of the present invention contains a compound having a structure represented by the formula (1-1) (hereinafter, also referred to as “specific compound”).
本発明において、特定化合物が熱塩基発生剤であるとは、本発明の硬化性樹脂組成物により形成された層(好ましくは、溶剤を含む本発明の硬化性樹脂組成物を基材に適用し、100℃等の温度により加熱することにより上記溶剤の少なくとも一部を除去した層)を加熱した場合に、特定化合物が塩基を発生する化合物であることを意味する。
本発明において、特定化合物は、230℃、3時間の加熱による分解率が50モル%以上である化合物が好ましく、180℃、3時間の加熱による分解率が50モル%以上である化合物がより好ましい。
また本発明において、特定化合物は、100℃、3時間の加熱による分解率が10モル%以下である化合物が好ましい。
上記分解率は、下記方法により測定される。
硬化性樹脂組成物をガラス上に塗布し、100℃で1分間加熱乾燥して、硬化性樹脂組成物層を形成する。硬化性樹脂組成物の塗布量は乾燥後の膜厚が15μmとなるようにする。その後、硬化性樹脂組成物層に対し、例えば230℃、3時間の加熱による分解率を測定する場合には、230℃、3時間の加熱を行う。上記加熱温度及び加熱時間を適宜変更することにより、特定の加熱温度及び加熱時間の加熱による分解率の測定が可能である。加熱後の硬化性樹脂組成物層を、メタノール/THF=50/50(質量比)溶液に超音波を当てながら10分浸漬させる。上記溶液に抽出された抽出物をHPLC(高速液体クロマトグラフィ)にて分析することで特定化合物の分解率を以下の式より算出する。
特定化合物の分解率(モル%)=特定化合物の分解物量(mol)/加熱前の硬化性樹脂組成物層に含まれる特定化合物量(mol)×100
また、特定化合物は、後述する加熱工程における加熱により塩基を発生する化合物であることが好ましい。 From the viewpoint of the film strength of the obtained cured film, the specific compound is preferably a thermal base generator.
In the present invention, the specific compound is a thermosetting agent when a layer formed by the curable resin composition of the present invention (preferably, the curable resin composition of the present invention containing a solvent is applied to a base material. It means that the specific compound is a compound that generates a base when the layer (the layer from which at least a part of the solvent is removed) is heated by heating at a temperature of 100 ° C. or the like.
In the present invention, the specific compound is preferably a compound having a decomposition rate of 50 mol% or more by heating at 230 ° C. for 3 hours, and more preferably a compound having a decomposition rate of 50 mol% or more by heating at 180 ° C. for 3 hours. ..
Further, in the present invention, the specific compound is preferably a compound having a decomposition rate of 10 mol% or less by heating at 100 ° C. for 3 hours.
The decomposition rate is measured by the following method.
The curable resin composition is applied onto glass and dried by heating at 100 ° C. for 1 minute to form a curable resin composition layer. The amount of the curable resin composition applied is such that the film thickness after drying is 15 μm. Then, when measuring the decomposition rate of the curable resin composition layer by heating at 230 ° C. for 3 hours, for example, heating at 230 ° C. for 3 hours is performed. By appropriately changing the heating temperature and heating time, it is possible to measure the decomposition rate by heating at a specific heating temperature and heating time. The cured resin composition layer after heating is immersed in a methanol / THF = 50/50 (mass ratio) solution for 10 minutes while applying ultrasonic waves. The decomposition rate of the specific compound is calculated from the following formula by analyzing the extract extracted into the above solution by HPLC (high performance liquid chromatography).
Decomposition rate of specific compound (mol%) = Decomposition amount of specific compound (mol) / Amount of specific compound contained in the curable resin composition layer before heating (mol) × 100
Further, the specific compound is preferably a compound that generates a base by heating in a heating step described later.
上記分解温度は、硬化性樹脂組成物の固形分を耐圧カプセル中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。
上記分解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 decomposition temperature of the specific compound in the curable resin composition is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 120 ° C. or higher, and further preferably 140 ° C. or higher. preferable. As the upper limit, it is more preferably 450 ° C. or lower, more preferably 350 ° C. or lower, and further preferably 250 ° C. or lower.
The decomposition temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when the solid content of the curable resin composition is heated to 500 ° C. in a pressure-resistant capsule at 5 ° C./min.
Examples of the device used for measuring the decomposition temperature include Q2000 (manufactured by TA Instruments) and the like.
本明細書でいう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。pKaが小さいほど強い酸であることを示す。pKaは、特に断らない限り、ACD/ChemSketch(登録商標)による計算値とする。又は、日本化学会編「改定5版 化学便覧 基礎編」に掲載の値を参照してもよい。また、化合物が複数のpKaを有する場合、特段の記載がない限り、化合物のpKaとはその化合物における複数のpKaのうち最大の値をいう。 When the specific compound is a thermal base generator, the pKa of the conjugate acid of the base generated from the specific compound is preferably 8 or more, and more preferably 9 or more, from the viewpoint of the film strength of the obtained cured film. It is preferable, and more preferably 10 or more. The upper limit of the pKa is not particularly limited, but is preferably 16 or less.
The term "pKa" as used herein means a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is represented by its negative common logarithm pKa. The smaller the pKa, the stronger the acid. Unless otherwise specified, pKa is a value calculated by ACD / ChemSketch (registered trademark). Alternatively, the values published in "Revised 5th Edition Chemistry Handbook Basics" edited by the Chemical Society of Japan may be referred to. When the compound has a plurality of pKa, the pKa of the compound means the maximum value among the plurality of pKa in the compound, unless otherwise specified.
-Ar-
式(1-1)中、Arは芳香族複素環構造を表す。
Arで表される芳香族複素環構造は、ピロール環構造、ピラゾール環構造、イミダゾール環構造、トリアゾール環構造、テトラゾール環構造等の5員環構造、アゾニン環等の9員環構造、又は、インドール環構造、イソインドール環構造、ベンゾイミダゾール環構造、インダゾール環構造、ベンゾトリアゾール環構造、プリン環構造、カルバゾール環構造等の多環式環構造であることが好ましく、5員環構造であることがより好ましく、ピラゾール環構造、イミダゾール環構造、トリアゾール環構造、又は、テトラゾール環構造であることが更に好ましく、ピラゾール環構造、イミダゾール環構造又はトリアゾール環構造であることが特に好ましい。これらの芳香族複素環構造に含まれる窒素原子のうち1つが、式(1-1)に記載された窒素原子である。
また、Arで表される複素環構造が上記多環式環構造である場合、インダゾール環構造又はベンゾイミダゾール環構造が好ましい。 [Structure represented by equation (1-1)]
-Ar-
In formula (1-1), Ar represents an aromatic heterocyclic structure.
The aromatic heterocyclic structure represented by Ar is a 5-membered ring structure such as a pyrazole ring structure, a pyrazole ring structure, an imidazole ring structure, a triazole ring structure or a tetrazole ring structure, a 9-membered ring structure such as an azonin ring, or an indole. A polycyclic ring structure such as a ring structure, an isoindole ring structure, a benzimidazole ring structure, an indazole ring structure, a benzotriazole ring structure, a purine ring structure, and a carbazole ring structure is preferable, and a 5-membered ring structure is preferable. It is more preferably a pyrazole ring structure, an imidazole ring structure, a triazole ring structure, or a tetrazole ring structure, and particularly preferably a pyrazole ring structure, an imidazole ring structure, or a triazole ring structure. One of the nitrogen atoms contained in these aromatic heterocyclic structures is the nitrogen atom represented by the formula (1-1).
When the heterocyclic structure represented by Ar is the polycyclic ring structure, an indazole ring structure or a benzimidazole ring structure is preferable.
式(1-1)中、*は芳香族環構造、脂肪族環構造、直鎖状若しくは分岐鎖状の不飽和炭化水素構造、又は、直鎖状若しくは分岐鎖状の飽和炭化水素構造との結合部位を表す。
上記芳香族環構造、脂肪族環構造、直鎖状若しくは分岐鎖状の不飽和炭化水素構造、又は、直鎖状若しくは分岐鎖状の飽和炭化水素構造は、本発明の効果が得られる範囲内において、それぞれ、置換基を有していてもよい。すなわち、式(1-1)で表される部分構造における*と結合する位置が芳香族環構造、脂肪族環構造、直鎖状若しくは分岐鎖状の不飽和炭化水素構造、又は、直鎖状若しくは分岐鎖状の飽和炭化水素構造であればよく、これらの構造は更に他の式(1-1)で表される構造、又は、式(1-1)で表される構造を含む他の構造と結合していてもよい。
上記芳香族環構造としては、芳香族炭化水素環構造であることが好ましく、炭素数6~20の芳香族炭化水素環構造であることがより好ましく、ベンゼン環構造であることが更に好ましい。
上記脂肪族環構造としては、炭素数6~20の脂肪族炭化水素環構造であることが好ましく、炭素数6~20の飽和脂肪族炭化水素環構造がより好ましく、シクロペンタン環構造、シクロヘキサン環構造等の単環飽和脂肪族炭化水素環構造、又は、ボルナン環構造、イソボルナン環構造、アダマンタン環構造、ジシクロペンタン環構造等の架橋飽和脂肪族炭化水素環構造がより好ましく、シクロヘキサン環又はアダマンチル環がより好ましい。
上記直鎖状若しくは分岐鎖状の不飽和炭化水素構造としては、エチニル基又はイソプロペニル基が好ましく、イソプロペニル基がより好ましい。
上記飽和炭化水素構造としては、炭素数1~20の飽和炭化水素構造が好ましく、炭素数1~4の飽和炭化水素構造がより好ましい。 -*-
In formula (1-1), * indicates an aromatic ring structure, an aliphatic ring structure, a linear or branched unsaturated hydrocarbon structure, or a linear or branched saturated hydrocarbon structure. Represents a binding site.
The above aromatic ring structure, aliphatic ring structure, linear or branched unsaturated hydrocarbon structure, or linear or branched saturated hydrocarbon structure is within the range in which the effect of the present invention can be obtained. Each may have a substituent. That is, the position where it is bonded to * in the partial structure represented by the formula (1-1) is an aromatic ring structure, an aliphatic ring structure, a linear or branched unsaturated hydrocarbon structure, or a linear structure. Alternatively, it may be a branched saturated hydrocarbon structure, and these structures are further represented by another formula (1-1) or another structure including a structure represented by the formula (1-1). It may be combined with the structure.
The aromatic ring structure is preferably an aromatic hydrocarbon ring structure, more preferably an aromatic hydrocarbon ring structure having 6 to 20 carbon atoms, and even more preferably a benzene ring structure.
The aliphatic ring structure is preferably an aliphatic hydrocarbon ring structure having 6 to 20 carbon atoms, more preferably a saturated aliphatic hydrocarbon ring structure having 6 to 20 carbon atoms, and a cyclopentane ring structure or a cyclohexane ring. A monocyclic saturated aliphatic hydrocarbon ring structure such as a structure, or a crosslinked saturated aliphatic hydrocarbon ring structure such as a Bornan ring structure, an isobornan ring structure, an adamantan ring structure, or a dicyclopentane ring structure is more preferable, and a cyclohexane ring or an adamantyl is more preferable. Rings are more preferred.
As the linear or branched unsaturated hydrocarbon structure, an ethynyl group or an isopropenyl group is preferable, and an isopropenyl group is more preferable.
As the saturated hydrocarbon structure, a saturated hydrocarbon structure having 1 to 20 carbon atoms is preferable, and a saturated hydrocarbon structure having 1 to 4 carbon atoms is more preferable.
特定化合物に含まれる、式(1-1)で表される構造の数は、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い。 -Number of structures represented by equation (1-1)-
The number of structures represented by the formula (1-1) contained in the specific compound is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
上記式(1-1)で表される構造は、下記式(1-2)で表される構造であることが好ましい。
The structure represented by the above formula (1-1) is preferably a structure represented by the following formula (1-2).
Z1~Z4のうち、0~3個が-N=であり、1~3個が-N=であることが好ましく、1個又は2個が-N=であることがより好ましい。
また、保存安定性の観点からは、Z1~Z4を含む5員環構造としては、トリアゾール環、ピラゾール環又はイミダゾール環が好ましく、ピラゾール環又はイミダゾール環がより好ましく、イミダゾール環が更に好ましい。
膜強度の観点からは、Z1~Z4を含む5員環構造としては、トリアゾール環、ピラゾール環又はイミダゾール環が好ましく、トリアゾール環又はピラゾール環が好ましく、トリアゾール環が更に好ましい。 -Z 1 ~ Z 4 -
Of Z 1 to Z 4 , 0 to 3 are preferably −N =, 1 to 3 are preferably −N =, and 1 or 2 are more preferably −N =.
From the viewpoint of storage stability, the 5-membered ring structure containing Z 1 to Z 4 is preferably a triazole ring, a pyrazole ring or an imidazole ring, more preferably a pyrazole ring or an imidazole ring, and further preferably an imidazole ring.
From the viewpoint of membrane strength, the 5-membered ring structure containing Z 1 to Z 4 is preferably a triazole ring, a pyrazole ring or an imidazole ring, preferably a triazole ring or a pyrazole ring, and more preferably a triazole ring.
また、Z1~Z4における-CRC=におけるRcは、水素原子、アルキル基、アリール基、カルボキシ基、又は、アルキルオキシカルボニル基であることが好ましく、水素原子又は炭素数1~4のアルキル基がより好ましく、水素原子が更に好ましい。
Rcにおけるアルキル基は、炭素数1~20のアルキル基が好ましく、炭素数1~10のアルキル基がより好ましく、炭素数1~4のアルキル基が更に好ましい。上記アルキル基における水素原子は、本発明の効果が得られる範囲内において、ハロゲン原子等の公知の置換基により置換されていてもよい。
Rcにおけるアリール基は、炭素数6~20のアリール基が好ましく、フェニル基がより好ましい。上記アリール基における水素原子は、本発明の効果が得られる範囲内において、公知の置換基により置換されていてもよい。
Rcにおけるアミノ基は、公知の置換基により置換されていてもよい。例えば、ジアルキルアミノ基、ジアリールアミノ基等が挙げられる。上記ジアルキルアミノ基におけるアルキル基の好ましい態様は、上述のRCにおけるアルキル基の好ましい態様と同様である。上記ジアリールアミノ基におけるアリール基の好ましい態様は、上述のRcにおけるアリール基の好ましい態様と同様である。
Rcにおけるアルキルオキシカルボニル基におけるアルキル基の好ましい態様は、上述のRcにおけるアルキル基の好ましい態様と同様である。 -R C -
Further, R c at −CR C = in Z 1 to Z 4 is preferably a hydrogen atom, an alkyl group, an aryl group, a carboxy group, or an alkyloxycarbonyl group, and has a hydrogen atom or 1 to 4 carbon atoms. Alkyl groups are more preferred, and hydrogen atoms are even more preferred.
The alkyl group in R c is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The hydrogen atom in the alkyl group may be substituted with a known substituent such as a halogen atom within the range in which the effect of the present invention can be obtained.
Aryl group in R c is preferably an aryl group having 6 to 20 carbon atoms, a phenyl group is more preferable. The hydrogen atom in the aryl group may be substituted with a known substituent within the range in which the effect of the present invention can be obtained.
Amino group in R c is optionally substituted by a known substituent. For example, a dialkylamino group, a diarylamino group and the like can be mentioned. The preferred embodiment of the alkyl group in the dialkylamino group is the same as the preferred embodiment of the alkyl group in RC described above. A preferred embodiment of the aryl group in the diarylamino group are the same as the preferred embodiment of the aryl group in the above R c.
A preferred embodiment of the alkyl group in the alkyloxycarbonyl group for R c is the same as the preferred embodiment of the alkyl group in the above R c.
上記芳香族複素環としては、複素原子として窒素原子を有する芳香族複素環であることが好ましい。また、上記芳香族複素環の環員数は、5又は6であることが好ましく、6であることが更に好ましい。
また、保存安定性の観点からは、2以上のRcが環構造を形成しない態様も好ましい態様である。 In the formula (1-2), among the Z 1 ~ Z 4, when two or more are -CR C =, 2 or more R C may be bonded to form a ring structure. The ring structure to be formed is preferably an aromatic hydrocarbon ring or an aromatic heterocycle, more preferably an aromatic hydrocarbon ring, and even more preferably a benzene ring.
The aromatic heterocycle is preferably an aromatic heterocycle having a nitrogen atom as a complex atom. The number of ring members of the aromatic heterocycle is preferably 5 or 6, and more preferably 6.
Further, from the viewpoint of storage stability, a mode in which two or more Rc do not form a ring structure is also a preferable mode.
式(1-2)中、*は式(1-1)中の*と同義であり、好ましい態様も同様である。 -*-
In formula (1-2), * is synonymous with * in formula (1-1), and the preferred embodiment is also the same.
特定化合物は、下記式(1-3)で表される化合物であることが好ましい。
The specific compound is preferably a compound represented by the following formula (1-3).
また、式(1-3)中、nが1である場合、X1は1価の有機基を表し、アルキル基、アリール基、又は(メタ)アクリロイル基であることが好ましく、環状アルキル基、アリール基又は(メタ)アクリロイル基であることがより好ましい。
本明細書において、単に「脂肪族炭化水素基」又は「アルキル基」と記載した場合、直鎖状、分岐鎖状、環状又はこれらの組み合わせにより形成される脂肪族炭化水素基又はアルキル基の全てが含まれるものとする。
上記アルキル基としては、炭素数1~20のアルキル基が好ましく、炭素数6~20の環状アルキル基がより好ましく、シクロへキシル基、又は、アダマンチル基が更に好ましい。
上記アリール基としては、フェニル基がより好ましい。 -X 1-
Further, in the formula (1-3), when n is 1, X 1 represents a monovalent organic group, preferably an alkyl group, an aryl group, or a (meth) acryloyl group, and a cyclic alkyl group, More preferably, it is an aryl group or a (meth) acryloyl group.
In the present specification, when simply referred to as "aliphatic hydrocarbon group" or "alkyl group", all of the aliphatic hydrocarbon groups or alkyl groups formed by linear, branched, cyclic or a combination thereof. Shall be included.
As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, a cyclic alkyl group having 6 to 20 carbon atoms is more preferable, and a cyclohexyl group or an adamantyl group is further preferable.
As the aryl group, a phenyl group is more preferable.
上記脂肪族環構造としては、シクロヘキサン環等の脂肪族飽和炭化水素環構造が好ましい。
上記芳香族環構造としては、ベンゼン環構造が好ましい。
また、X1は脂肪族環構造、又は、芳香族環構造が2以上結合した基であってもよい。このような基の例としては、下記式(X-1)で表される基が好ましい。
式(X-1)中、L1は単結合又は脂肪族炭化水素基、芳香族炭化水素基、-C-、-C(=O)-、-S-、-S(=O)2-、-NRN-、若しくはこれらが2以上結合した基であることが好ましい。上記RNは水素原子又は炭化水素基であり、水素原子、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好ましく、水素原子又はメチル基であることが更に好ましく、水素原子であることが特に好ましい。
上記脂肪族炭化水素基は、飽和脂肪族炭化水素基であることが好ましく、炭素数1~20の飽和脂肪族炭化水素基であることがより好ましく、炭素数1~10の飽和脂肪族炭化水素基であることが更に好ましい。
上記脂肪族炭化水素基は置換基を有していてもよく、置換基としては、芳香族炭化水素基、ハロゲン原子等が挙げられる。
上記芳香族炭化水素基は、炭素数6~20の芳香族炭化水素基であることが好ましく、炭素数6~12の芳香族炭化水素基であることがより好ましく、炭素数6の芳香族炭化水素基であることが更に好ましい。
上記芳香族炭化水素基は置換基を有していてもよく、置換基としては、脂肪族炭化水素基、芳香族炭化水素基、ハロゲン原子等が挙げられる。
式(X-1)中、aは1~5の整数を表し、1又は2であることが好ましく、1であることがより好ましい。
式(X-1)中、bは2~10の整数であることが好ましく、2~6の整数であることがより好ましく、2又は3であることがより好ましい。 In formula (1-3), when n is 2 or more, X 1 represents an organic group having a valence of 2 or more, and is a group obtained by removing n hydrogen atoms from the aliphatic ring structure or the aromatic ring structure. More preferably, it is a group obtained by removing n hydrogen atoms from the aliphatic hydrocarbon ring structure or the aromatic hydrocarbon ring structure, and n hydrogen atoms are removed from the aromatic hydrocarbon ring structure. It is more preferably a hydrocarbon group.
As the aliphatic ring structure, an aliphatic saturated hydrocarbon ring structure such as a cyclohexane ring is preferable.
As the aromatic ring structure, a benzene ring structure is preferable.
Further, X 1 may be an aliphatic ring structure or a group in which two or more aromatic ring structures are bonded. As an example of such a group, a group represented by the following formula (X-1) is preferable.
In formula (X-1), L 1 is a single bond or an aliphatic hydrocarbon group, an aromatic hydrocarbon group, -C-, -C (= O)-, -S-, -S (= O) 2- , -NR N- , or a group in which two or more of these are bonded is preferable. The RN is a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and more preferably a hydrogen atom or a methyl group. , A hydrogen atom is particularly preferable.
The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms. It is more preferably a group.
The aliphatic hydrocarbon group may have a substituent, and examples of the substituent include an aromatic hydrocarbon group and a halogen atom.
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 carbon atoms. It is more preferably a hydrogen group.
The aromatic hydrocarbon group may have a substituent, and examples of the substituent include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a halogen atom.
In the formula (X-1), a represents an integer of 1 to 5, preferably 1 or 2, and more preferably 1.
In the formula (X-1), b is preferably an integer of 2 to 10, more preferably an integer of 2 to 6, and more preferably 2 or 3.
また、X1における、式(1-3)に記載されたn個のカルボニル基(-C(=O)-)との結合部位が、いずれも芳香族炭化水素環構造であることが好ましい
nが1である場合、X1はフェニル基が好ましい。
nが2以上である場合、X1はベンゼン環構造から2以上の水素原子を除いた構造、又は、上述の式(X-1)で表される基が好ましい
上記芳香族炭化水素環構造としては、ベンゼン環構造が好ましい。 From the viewpoint of chemical resistance, X 1 preferably contains an aromatic hydrocarbon ring structure, and more preferably is a group obtained by removing n hydrogen atoms from the aromatic hydrocarbon ring structure.
Further, it is preferable that the binding sites of X 1 with the n carbonyl groups (−C (= O) −) described in the formula (1-3) are all aromatic hydrocarbon ring structures. When is 1, X 1 is preferably a phenyl group.
When n is 2 or more, X 1 is preferably a structure obtained by removing 2 or more hydrogen atoms from the benzene ring structure, or a group represented by the above formula (X-1) as the above aromatic hydrocarbon ring structure. Preferably has a benzene ring structure.
式(1-3)中、Z1~Z4及びRCはそれぞれ、式(1-2)におけるZ1~Z4及びRCと同義であり、好ましい態様も同様である。 -Z 1 ~ Z 4, R C -
Wherein (1-3), Z 1 ~ Z 4 and R C are each the same meaning as Z 1 ~ Z 4 and R C in formula (1-2), preferable embodiments thereof are also the same.
式(1-3)中、nは1~10の整数であることが好ましく、1~4の整数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い。 -N-
In the formula (1-3), n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.
硬化膜の膜強度の観点からは、特定化合物の分子量は、90~2,000であることが好ましく、90~1,000であることがより好ましく、90~500であることが更に好ましく、100~400であることが特に好ましい。 [Molecular weight]
From the viewpoint of the film strength of the cured film, the molecular weight of the specific compound is preferably 90 to 2,000, more preferably 90 to 1,000, further preferably 90 to 500, and 100. It is particularly preferably about 400.
特定化合物の具体例としては、下記式(BG-1)~式(BG-16)で表される化合物におけるアニオン部が挙げられるが、これに限定されるものではない。 〔Concrete example〕
Specific examples of the specific compound include, but are not limited to, the anion moiety in the compounds represented by the following formulas (BG-1) to (BG-16).
特定化合物の含有量は、組成物の保存安定性及び得られる硬化膜の破断伸び率を向上する等の観点からは、硬化性樹脂組成物の全固形分に対し、0.005~50質量%であることが好ましい。下限は、0.05質量%以上がより好ましく、0.5質量%以上が更に好ましく、1質量%以上が特に好ましい。上限は、金属(例えば、配線などに用いられる銅)の耐腐食性等の観点からは、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%以下が特に好ましい。
また、複素環含有ポリマー前駆体100質量部に対する特定化合物の含有量は、組成物の保存安定性及び得られる硬化膜の破断伸び率を向上する等の観点からは、0.005質量部以上であることが好ましく、0.06質量部以上であることがより好ましく、0.5質量部以上であることが更に好ましく、1質量部以上であることが更に好ましい。上限は、金属(例えば、配線などに用いられる銅)の耐腐食性等の観点からは、例えば、20質量部以下であることが好ましく、15質量部以下であることがより好ましく、10質量部以下であることが更に好ましく、7.5質量部以下であることが特に好ましい。
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 0.005 to 50% by mass with respect to the total solid content of the curable resin composition from the viewpoint of improving the storage stability of the composition and the elongation at break of the obtained cured film. Is preferable. The lower limit is more preferably 0.05% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. The upper limit is more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less, from the viewpoint of corrosion resistance of a metal (for example, copper used for wiring or the like).
The content of the specific compound with respect to 100 parts by mass of the heterocyclic polymer precursor is 0.005 parts by mass or more from the viewpoint of improving the storage stability of the composition and the elongation at break of the obtained cured film. It is preferably 0.06 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 1 part by mass or more. From the viewpoint of corrosion resistance of metal (for example, copper used for wiring and the like), the upper limit is preferably, for example, 20 parts by mass or less, more preferably 15 parts by mass or less, and 10 parts by mass. It is more preferably less than or equal to 7.5 parts by mass or less.
As the specific compound, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
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。
また、本発明では、オニウム塩を実質的に含まない構成とすることもできる。実質的に含まないとは、本発明の硬化性樹脂組成物において、オニウム塩の含有量が、硬化性樹脂組成物の全固形分に対して5質量%以下であることをいい、好ましくは3質量%以下、より好ましくは1質量%であることをいう。
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.
Further, in the present invention, the structure may be substantially free of onium salts. The term "substantially free" means that the content of the onium salt in the curable resin composition of the present invention is 5% by mass or less based on the total solid content of the curable resin composition, preferably 3 It means that it is 1% by mass or less, more preferably 1% by mass.
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 the anion may or may not be bonded via a covalent bond. ..
That is, the onium salt may be an intermolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are different 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。
As the ammonium cation, a quaternary ammonium cation is preferable.
The ammonium cation is preferably a cation represented by the following formula (101).
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 group. 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 sulfate anion is preferable, and a carboxylic acid anion is more preferable because both the stability of the salt and the thermal decomposability 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.
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 the substituent constant σm of Hammett shows a positive value. Here, σm is a review article 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).
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、特定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。 From the viewpoint that the cyclization of the specific precursor is easily carried out at a low temperature and the storage stability of the curable resin composition is easily improved, the onium salt in the present invention contains an ammonium cation as a cation, and the onium salt is an anion. As a result, it is preferable to contain an anion having a 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 specific precursor or the like is improved. Is more preferable.
The above pKa includes Determination of Organic Strategies by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O., Nachod, F. See Nachod, FC; 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 have the same meaning as 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)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 the formula (Y1-3), 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 (Y1-3), 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.
Each of R 8 to R 10 is preferably an alkyl group or an aryl group independently, 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 group. 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 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 diallyl 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 group. 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 independently represent a hydrogen atom or a hydrocarbon group.
Each of R 13 to R 16 is preferably an alkyl group or an aryl group independently, 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 group. 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 based on 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 kinds are used, the total amount is preferably in the above range.
本発明の硬化性樹脂組成物は、上述の他の熱塩基発生剤を更に含んでもよい。
また、本発明では、他の熱塩基発生剤を実質的に含まない構成とすることもできる。実質的に含まないとは、本発明の硬化性樹脂組成物において、他の熱塩基発生剤の含有量が、硬化性樹脂組成物の全固形分に対して5質量%以下であることをいい、好ましくは3質量%以下、より好ましくは1質量%であることをいう。
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 the above-mentioned other thermosetting agents.
Further, in the present invention, a configuration that does not substantially contain other thermobase generators can be used. The term "substantially free" means that the content of the other thermosetting agent in the curable resin composition of the present invention is 5% by mass or less based on the total solid content of the curable resin composition. It means that it is preferably 3% by mass or less, and more preferably 1% by mass.
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), and 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 effects of the present invention are 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), aryl group (6 to 22 carbon atoms are preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7). ~ 19 is more preferable, and 7 to 11 is more preferable), and a hydrogen atom or a methyl group is preferable.
Rb 17 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), 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.
また、本発明の硬化性樹脂組成物は、下記式(TBG-1)又は下記式(TBG-2)で表されるアニオン(以下、「特定アニオン」ともいう。)を熱塩基発生剤として含んでもよい。
本発明の硬化性樹脂組成物において、特定アニオンは、後述する有機カチオン等のカチオンと塩構造を形成していてもよいし、解離してアニオンの状態で存在していてもよい。
また、本発明の硬化性樹脂組成物の調製時には、組成物に特定アニオンと後述する有機カチオンとを含ませるため、特定アニオンと後述の有機カチオンの塩である化合物、又は上記化合物の溶液と、複素環含有ポリマー等の組成物に含まれる他の成分と、を混合して調製してもよい。
Further, the curable resin composition of the present invention contains an anion represented by the following formula (TBG-1) or the following formula (TBG-2) (hereinafter, also referred to as "specific anion") as a thermobase generator. It may be.
In the curable resin composition of the present invention, the specific anion may form a salt structure with a cation such as an organic cation described later, or may be dissociated and exist in an anion state.
Further, at the time of preparing the curable resin composition of the present invention, in order to include the specific anion and the organic cation described later in the composition, a compound which is a salt of the specific anion and the organic cation described later, or a solution of the above compound is used. It may be prepared by mixing with other components contained in the composition such as a heterocyclic ring-containing polymer.
上記含窒素脂肪族環構造、又は、上記含窒素芳香環構造に含まれる窒素原子のうち少なくとも1つは、式(TBG-1)に記載されたR11及びR12が結合する窒素原子である。 Further, R 11 and R 12 may be combined to form a ring structure, and the ring structures formed include a pyrrolidine ring structure, an imidazolidine ring structure, a pyrazoledin ring structure, a piperidine ring structure, a piperazine ring structure, and morpholin. Examples thereof include a nitrogen-containing aliphatic ring structure such as a ring structure, a pyrrol ring structure, an imidazole ring structure, a pyridine ring structure, a pyrazine ring structure, a pyrimidine ring structure, and a nitrogen-containing aromatic ring structure such as a pyridazine ring structure.
At least one of the nitrogen atoms contained in the nitrogen-containing aliphatic ring structure or the nitrogen-containing aromatic ring structure is a nitrogen atom to which R 11 and R 12 described in the formula (TBG-1) are bonded. ..
置換基としては、本発明の効果が得られる限りにおいて公知の置換基を有することができるが、例えば、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、R11及びR12のうち少なくとも一方、又は、R11及びR12が結合して形成された環構造は、置換基としてエチレン性不飽和結合を有する基を有していてもよい。
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)アクリロイル基、上述の式(III)で表される基などが挙げられる。 Further, at least one of R 11 and R 12, or ring structure and R 11 and R 12 are formed by bonding, it may further have a substituent.
As the substituent, a known substituent can be used as long as the effect of the present invention can be obtained, and examples thereof include an alkyl group, an aryl group, and a halogen atom.
Further, at least one of R 11 and R 12, or ring structure and R 11 and R 12 are formed by bonding may have a group having an ethylenically unsaturated bond as a substituent.
Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acryloyl group, and the above formula. Examples thereof include the group represented by (III).
本発明の硬化性樹脂組成物は、特定アニオンと有機カチオンの塩である化合物を含有してもよい。
特定アニオンと有機カチオンの塩である化合物は、硬化性樹脂組成物において、特定アニオンと有機カチオンの塩として存在していてもよいし、特定アニオンと有機カチオンに解離していてもよい。
例えば、20℃等の保管時には特定アニオンと有機カチオンの塩として存在し、180℃等の加熱時には、特定アニオンと有機カチオンとが解離する化合物であってもよい。また、上記加熱時には、更に特定アニオンが分解し、塩基を発生することが好ましい。
有機カチオンとしては、特に限定されないが、1価の有機カチオンであることが好ましい。
また、有機カチオンは、アンモニウムカチオン、イミニウムカチオン、又はホスホニウムカチオンであることが好ましい。 -Organic cation-
The curable resin composition of the present invention may contain a compound which is a salt of a specific anion and an organic cation.
The compound which is a salt of the specific anion and the organic cation may be present as a salt of the specific anion and the organic cation in the curable resin composition, or may be dissociated into the specific anion and the organic cation.
For example, it may be a compound that exists as a salt of a specific anion and an organic cation when stored at 20 ° C. or the like, and dissociates the specific anion and the organic cation when heated at 180 ° C. or the like. Further, it is preferable that the specific anion is further decomposed to generate a base during the above heating.
The organic cation is not particularly limited, but is preferably a monovalent organic cation.
The organic cation is preferably an ammonium cation, an iminium cation, or a phosphonium cation.
その他、有機カチオンとしては、後述するオニウム塩の説明におけるアンモニウムカチオン、イミニウムカチオン又はホスホニウムカチオンも好適に用いることができる。 Specific examples of the organic cation include, but are not limited to, the anion moiety in the compounds represented by the formulas (BA-1) to (BA-22) described later.
In addition, as the organic cation, an ammonium cation, an iminium cation, or a phosphonium cation described later in the description of the onium salt can also be preferably used.
特定アニオンと有機カチオンの塩である化合物の含有量は、組成物の保存安定性及び得られる硬化膜の破断伸び率を向上する等の観点からは、硬化性樹脂組成物の全固形分に対し、0.005~50質量%であることが好ましい。下限は、0.05質量%以上がより好ましく、0.5質量%以上が更に好ましく、1質量%以上が特に好ましい。上限は、金属(例えば、配線などに用いられる銅)の耐腐食性等の観点からは、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%以下が特に好ましい。
また、複素環含有ポリマー前駆体100質量部に対する特定アニオンと有機カチオンの塩である化合物の含有量は、組成物の保存安定性及び得られる硬化膜の破断伸び率を向上する等の観点からは、0.005質量部以上であることが好ましく、0.06質量部以上であることがより好ましく、0.5質量部以上であることが更に好ましく、1質量部以上であることが更に好ましい。上限は、金属(例えば、配線などに用いられる銅)の耐腐食性等の観点からは、例えば、20質量部以下であることが好ましく、15質量部以下であることがより好ましく、10質量部以下であることが更に好ましく、7.5質量部以下であることが特に好ましい。
また、本発明では、特定アニオンと有機カチオンの塩である化合物を実質的に含まない構成とすることもできる。実質的に含まないとは、本発明の硬化性樹脂組成物において、他の熱塩基発生剤の含有量が、硬化性樹脂組成物の全固形分に対して5質量%以下であることをいい、好ましくは3質量%以下、より好ましくは1質量%であることをいう。
特定アニオンと有機カチオンの塩である化合物は、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 compound, which is a salt of the specific anion and the organic cation, is based on the total solid content of the curable resin composition from the viewpoint of improving the storage stability of the composition and the elongation at break of the obtained cured film. , 0.005 to 50% by mass is preferable. The lower limit is more preferably 0.05% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. The upper limit is more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less, from the viewpoint of corrosion resistance of a metal (for example, copper used for wiring or the like).
Further, the content of the compound which is a salt of the specific anion and the organic cation with respect to 100 parts by mass of the heterocyclic-containing polymer precursor is from the viewpoint of improving the storage stability of the composition and the breaking elongation rate of the obtained cured film. , 0.005 parts by mass or more, more preferably 0.06 parts by mass or more, further preferably 0.5 parts by mass or more, and further preferably 1 part by mass or more. From the viewpoint of corrosion resistance of metal (for example, copper used for wiring and the like), the upper limit is preferably, for example, 20 parts by mass or less, more preferably 15 parts by mass or less, and 10 parts by mass. It is more preferably less than or equal to 7.5 parts by mass or less.
Further, in the present invention, the composition may be substantially free of a compound which is a salt of a specific anion and an organic cation. The term "substantially free" means that the content of the other thermosetting agent in the curable resin composition of the present invention is 5% by mass or less based on the total solid content of the curable resin composition. It means that it is preferably 3% by mass or less, and more preferably 1% by mass.
As the compound which is a salt of a specific anion and an organic cation, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
本発明の硬化性樹脂組成物は、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 curable resin composition of the present invention preferably contains a photopolymerization initiator.
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 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.
本発明の硬化性樹脂組成物は、重合開始剤として熱重合開始剤を含んでもよく、とく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、複素環含有ポリマー前駆体の環化と共に、複素環含有ポリマー前駆体の重合反応を進行させることもできるので、より高度な耐熱化が達成できることとなる。 <Thermal polymerization initiator>
The curable resin composition of the present invention may contain a thermal polymerization initiator as the polymerization initiator, and may particularly contain 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 heterocyclic polymer precursor can be allowed to proceed as well as the cyclization of the heterocyclic polymer precursor, so that higher heat resistance can be achieved.
〔ラジカル重合性化合物〕
本発明の硬化性樹脂組成物は、重合性化合物を更に含むことが好ましい。
重合性化合物としては、ラジカル重合性化合物を用いることができる。ラジカル重合性化合物は、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、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。ラジカル重合性基は、(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。 <Polymerizable compound>
[Radical polymerizable compound]
The curable resin composition of the present invention preferably further contains a polymerizable compound.
As the polymerizable compound, a radically polymerizable compound can be used. The radically polymerizable compound is a compound having a radically polymerizable group. Examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group. The radically polymerizable group is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.
本発明の硬化性樹脂組成物は、上述したラジカル重合性化合物以外の重合性化合物を更に含むことができる。上述したラジカル重合性化合物以外の重合性化合物としては、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;ベンゾオキサジン化合物が挙げられる。 [Polymerizable compounds other than the radically polymerizable compounds described above]
The curable resin composition of the present invention can further contain a polymerizable compound other than the radically polymerizable compound described above. Examples of the polymerizable compound other than the above-mentioned radically polymerizable compound include a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound.
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としては、下記式(AM1)、(AM4)又は(AM5)で示される化合物が好ましい。 -Compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group-
As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferable.
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 compounds (compounds with epoxy groups)-
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the 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 ring-opening addition reaction, degassing does not occur during curing, and the heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.
本発明の硬化性樹脂組成物は、溶剤を含有することが好ましい。溶剤は、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、アミド類などの化合物が挙げられる。 <Solvent>
The curable resin composition of the present invention preferably 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, and amides.
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。 <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.
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 adhesiveness improving agent include a silane coupling agent.
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、熱酸発生剤、N-フェニルジエタノールアミンなどの増感剤、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 can be used with various additives such as a thermoacid generator, a sensitizer such as N-phenyldiethanolamine, and a chain transfer agent, if necessary, as long as the effects of the present invention can be obtained. , Surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, antiaggregating agents 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、N-フェニルジエタノールアミン等の増感剤が挙げられる。
また、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 electron-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.
Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine.
Moreover, you may use a sensitizing dye as a sensitizer.
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。
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.
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。 <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.
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. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. 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.
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.
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.
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 film (d) Heating step for heating the developed film at 50 to 450 ° C. By heating in the 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.
<膜形成工程(層形成工程)>
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。 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). In particular, it is preferable to perform each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order. By laminating the cured film in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film, between the cured films, or both. In the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to (d). ) Can be performed a plurality of times to obtain a laminated body of the cured film.
<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、基材としては、例えば板状の基材(基板)が用いられる。 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 transistor. There are no particular restrictions on magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, and plasma display panel (PDP) electrode plates. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material is more preferable.
Further, as the base material, for example, a plate-shaped base material (board) is used.
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。 Specifically, as the means to apply, the dip coating method, the air knife coating method, the curtain coating method, the wire bar coating method, the gravure coating method, the extrusion coating method, the spray coating method, the spin coating method, the slit coating method, etc. 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 used. 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, 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.
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 .
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、パドル、スプレー、浸漬、超音波等の現像方法が採用可能である。 <Development process>
The production method of the present invention may include a developing step of developing (developing the above film) the exposed film (curable resin composition layer). By performing the development, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.
本発明において、現像液としてアルカリ現像液を用いる場合をアルカリ現像、現像液として有機溶剤を50質量%以上含む現像液を用いる場合を溶剤現像という。 Development is performed using a developing solution. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
In the present invention, the case where an alkaline developer is used as the developer is called alkaline development, and the case where a developer containing 50% by mass or more of an organic solvent is used as the developer is called solvent development.
アルカリ現像における現像液は、pHが10~14である水溶液がより好ましい。
アルカリ現像における現像液に含まれるアルカリ化合物としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、ケイ酸ナトリウム、ケイ酸カリウム、メタケイ酸ナトリウム、メタケイ酸カリウム、アンモニア又はアミンなどが挙げられる。アミンとしては、例えば、エチルアミン、n-プロピルアミン、ジエチルアミン、ジ-n-プロピルアミン、トリエチルアミン、メチルジエチルアミン、アルカノールアミン、ジメチルエタノールアミン、トリエタノールアミン、四級アンモニウム水酸化物、水酸化テトラメチルアンモニウム(TMAH)、水酸化テトラエチルアンモニウム、水酸化テトラブチルアンモニウムなどが挙げられる。なかでも金属を含まないアルカリ化合物が好ましく、アミンがより好ましい。
アルカリ化合物は1種のみでもよいし、2種以上であってもよい。アルカリ化合物が2種以上である場合は、その合計が上記範囲であることが好ましい。 In alkaline development, the developer preferably has an organic solvent content of 10% by mass or less based on the total mass of the developer. The content is more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably not containing an organic solvent.
The developing solution in alkaline development is more preferably an aqueous solution having a pH of 10 to 14.
Examples of the alkaline compound contained in the developing solution in alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicate. Examples include potassium silicate, ammonia or amine. Examples of amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, and tetramethylammonium hydroxide. (TMAH), tetraethylammonium hydroxide, tetrabutylammonium hydroxide and the like can be mentioned. Of these, metal-free alkaline compounds are preferable, and amines are more preferable.
The alkaline compound may be only one kind or two or more kinds. When there are two or more alkaline compounds, the total is preferably in the above range.
本発明では、現像液は、ClogP値が-1~5の有機溶剤を含むことが好ましく、ClogP値が0~3の有機溶剤を含むことがより好ましい。ClogP値は、ChemBioDrawにて構造式を入力して計算値として求めることができる。 The developer used in solvent development preferably has 60% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and 90% by mass or more of an organic solvent with respect to the total mass of the developer. It is more preferably a solvent. Further, the developing solution may be 100% by mass of an organic solvent with respect to the total mass of the developing solution.
In the present invention, 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.
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、複素環含有ポリマー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複素環含有ポリマー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、未反応の複素環含有ポリマー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 heterocyclic polymer precursor proceeds. Further, the curable resin composition of the present invention may contain a radically polymerizable compound other than the heterocyclic polymer precursor, but may also cure a radically polymerizable compound other than the unreacted heterocyclic polymer precursor. 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.
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、本実施例における化合物BG-1~BG-16は、上述の具体例における化合物BG-1~BG-16と同様である。 Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.
Further, the compounds BG-1 to BG-16 in this example are the same as the compounds BG-1 to BG-16 in the above-mentioned specific example.
〔A-1:オキシジフタル酸二無水物、4,4’-ビフタル酸無水物、2-ヒドロキシエチルメタクリレートおよび4,4’-ジアミノジフェニルエーテルからのポリイミド前駆体樹脂A-1の合成〕
撹拌機、コンデンサー及び内部温度計を取りつけた平底ジョイントを備えた乾燥反応器中で水分を除去しながら、4,4’-ビフタル酸無水物 9.49g(32.25ミリモル)、オキシジフタル酸二無水物 10.0g(32.25ミリモル)をジグリム 140mL中に懸濁させた。2-ヒドロキシエチルメタクリレート 16.8g(129ミリモル)、ヒドロキノン 0.05gおよびピリジン 10.7g(135ミリモル)を続いて添加し、60℃の温度で18時間撹拌した。次いで、混合物を-20℃まで冷却した後、塩化チオニル 16.1g(135.5ミリモル)を90分かけて滴下した。ピリジニウムヒドロクロリドの白色沈澱が得られた。次いで、混合物を室温まで温め、2時間撹拌した後、ピリジン 9.7g(123ミリモル)およびN-メチルピロリドン(NMP) 25mLを添加し、透明溶液を得た。次いで、得られた透明液体に、4,4’-ジアミノジフェニルエーテル 11.8g(58.7ミリモル)をNMP 100mL中に溶解させたものを、1時間かけて滴下により添加した。次いで、メタノール 5.6g(17.5ミリモル)と3,5-ジ-tert-ブチル-4-ヒドロキシトルエン 0.05gを加え、混合物を2時間撹拌した。次いで、4リットルの水の中でポリイミド前駆体樹脂を沈殿させ、水-ポリイミド前駆体樹脂混合物を500rpmの速度で15分間撹拌した。ポリイミド前駆体樹脂を濾過して取得し、4リットルの水の中で再度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樹脂を減圧下、45℃で3日間乾燥した。得られたポリイミド前駆体A-1の重量平均分子量は24,800、数平均分子量は10,500であった。 <Synthesis example 1>
[A-1: Synthesis of polyimide precursor resin A-1 from oxydiphthalic anhydride, 4,4'-biphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether]
9.49 g (32.25 mmol) of 4,4'-biphthalic anhydride, oxydiphthalic dianhydride while removing water in a drying reactor with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. 10.0 g (32.25 mmol) of the product was suspended in 140 mL of diglyme. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 18 hours. The mixture was then cooled to −20 ° C. and then 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature, stirred for 2 hours and then added 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) to give a clear solution. Then, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added to the obtained transparent liquid by dropping over 1 hour. Then 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 3 days. The obtained polyimide precursor A-1 had a weight average molecular weight of 24,800 and a number average molecular weight of 10,500.
〔A-2:オキシジフタル酸二無水物、2-ヒドロキシエチルメタクリレートおよび4,4’-ジアミノジフェニルエーテルからのポリイミド前駆体樹脂A-2の合成〕
撹拌機、コンデンサーおよび内部温度計を取りつけた平底ジョイントを備えた乾燥反応器中で水分を除去しながら、オキシジフタル酸二無水物 20.0g(64.5ミリモル)をジグリム140mL中に懸濁させた。2-ヒドロキシエチルメタクリレート 16.8g(129ミリモル)、ヒドロキノン 0.05gおよびピリジン 10.7g(135ミリモル)を続いて添加し、60℃の温度で18時間撹拌した。次いで、混合物を-20℃まで冷却した後、塩化チオニル 16.1g(135.5ミリモル)を90分かけて滴下した。ピリジニウムヒドロクロリドの白色沈澱が得られた。次いで、混合物を室温まで温め、2時間撹拌した後、ピリジン 9.7g(123ミリモル)およびN-メチルピロリドン(NMP) 25mLを添加し、透明溶液を得た。次いで、得られた透明液体に、4,4’-ジアミノジフェニルエーテル 11.8g(58.7ミリモル)をNMP 100mL中に溶解させたものを、1時間かけて滴下により添加した。次いで、メタノール 5.6g(17.5ミリモル)と3,5-ジ-tert-ブチル-4-ヒドロキシトルエン 0.05gを加え、混合物を2時間撹拌した。次いで、4リットルの水の中でポリイミド前駆体樹脂を沈殿させ、水-ポリイミド前駆体樹脂混合物を500rpmの速度で15分間撹拌した。ポリイミド前駆体樹脂を濾過して取得し、4リットルの水の中で再度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樹脂を減圧下で、45℃で3日間乾燥した。得られたポリイミド前駆体A-2の重量平均分子量は23,500、数平均分子量は8,800であった。 <Synthesis example 2>
[A-2: Synthesis of polyimide precursor resin A-2 from oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether]
20.0 g (64.5 mmol) of oxydiphthalic dianhydride was suspended in 140 mL of diglyme while removing water in a drying reactor with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. .. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 18 hours. The mixture was then cooled to −20 ° C. and then 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature, stirred for 2 hours and then added 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) to give a clear solution. Then, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added to the obtained transparent liquid by dropping over 1 hour. Then 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 3 days. The weight average molecular weight of the obtained polyimide precursor A-2 was 23,500, and the number average molecular weight was 8,800.
〔A-3:オキシジフタル酸二無水物、2-ヒドロキシエチルメタクリレート、4,4’-オキシビス(ベンゾイルクロリド)及び4,4’-ジアミノジフェニルエーテルからのポリアミドイミド前駆体A-3の合成〕
撹拌機、コンデンサーおよび内部温度計を取りつけた平底ジョイントを備えた乾燥反応器中で水分を除去しながら、オキシジフタル酸二無水物 16.0g(51.6ミリモル)をジグリム 140mL中に懸濁させた。2-ヒドロキシエチルメタクリレート 13.5g(103ミリモル)、ヒドロキノン 0.05gおよびピリジン 10.7g(135ミリモル)を続いて添加し、60℃の温度で18時間撹拌した。次いで、混合物を-20℃まで冷却した後、塩化チオニル 12.9g(108ミリモル)を90分かけて滴下した。ピリジニウムヒドロクロリドの白色沈澱が得られた。次いで、混合物を室温まで温め、2時間撹拌した後、ピリジン 9.7g(123ミリモル)、4,4’-オキシビス(ベンゾイルクロリド) 3.81g(12.9ミリモル)およびN-メチルピロリドン(NMP) 25mLを添加し、透明溶液を得た。次いで、得られた透明液体に、4,4’-ジアミノジフェニルエーテル 11.8g(59ミリモル)をNMP 100mL中に溶解させたものを、1時間かけて滴下により添加した。次いで、メタノール 5.6g(17.5ミリモル)と3,5-ジ-tert-ブチル-4-ヒドロキシトルエン 0.05gを加え、混合物を2時間撹拌した。次いで、4リットルの水の中でポリアミドイミド前駆体樹脂を沈殿させ、水-ポリアミドイミド前駆体樹脂混合物を500rpmの速度で15分間撹拌した。ポリアミドイミド前駆体樹脂を濾過して取得し、4リットルの水の中で再度30分間撹拌し再び濾過した。次いで、得られたポリアミドイミド前駆体樹脂を減圧下で、45℃で3日間乾燥した。得られたポリアミドイミド前駆体の重量平均分子量は23,800、数平均分子量は9,900であった。
[A-3: Synthesis of polyamide-imide precursor A-3 from oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate, 4,4'-oxybis (benzoyl chloride) and 4,4'-diaminodiphenyl ether]
16.0 g (51.6 mmol) of oxydiphthalic dianhydride was suspended in 140 mL of diglyme while removing water in a drying reactor with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. .. 13.5 g (103 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 18 hours. The mixture was then cooled to −20 ° C. and then 12.9 g (108 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature and stirred for 2 hours, after which 9.7 g (123 mmol) of pyridine, 3.81 g (12.9 mmol) of 4,4'-oxybis (benzoyl chloride) and N-methylpyrrolidone (NMP). 25 mL was added to give a clear solution. Then, 11.8 g (59 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added to the obtained transparent liquid by dropping over 1 hour. Then 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added and the mixture was stirred for 2 hours. The polyamide-imide precursor resin was then precipitated in 4 liters of water and the water-polyamideimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polyamide-imide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyamide-imide precursor resin was dried under reduced pressure at 45 ° C. for 3 days. The weight average molecular weight of the obtained polyamide-imide precursor was 23,800, and the number average molecular weight was 9,900.
〔A-4:2,2’-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、及び、4,4’-オキシジベンゾイルクロリドからのポリベンゾオキサゾール前駆体A-4の合成〕
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 28.0g(76.4ミリモル)をN-メチルピロリドン 200gに撹拌溶解した。続いて、ピリジン 12.1g(153ミリモル)を加え、温度を-10~0℃に保ちながら、N-メチルピロリドン 75gに4,4’-オキシジベンゾイルクロリド 20.7g(70.1ミリモル)を溶解させた溶液を1時間かけて滴下した。30分間撹拌した後、塩化アセチル 1.00g(12.7ミリモル)を加え、さらに60分間撹拌した。次いで、6リットルの水の中でポリベンゾオキサゾール前駆体樹脂を沈殿させ、水-ポリベンゾオキサゾール前駆体樹脂混合物を500rpmの速度で15分間撹拌した。ポリベンゾオキサゾール前駆体樹脂を濾過して取得し、6リットルの水の中で再度30分間撹拌し再び濾過した。次いで、得られたポリベンゾオキサゾール前駆体樹脂を減圧下で、45℃で3日間乾燥した。得られたポリベンゾオキサゾール前駆体A-4の重量平均分子量は21,500、数平均分子量は9,500であった。
[Synthesis of polybenzoxazole precursor A-4 from A-4: 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-oxydibenzoyl chloride]
28.0 g (76.4 mmol) of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 200 g of N-methylpyrrolidone with stirring. Subsequently, 12.1 g (153 mmol) of pyridine was added, and 20.7 g (70.1 mmol) of 4,4'-oxydibenzoyl chloride was added to 75 g of N-methylpyrrolidone while keeping the temperature at -10 to 0 ° C. The dissolved solution was added dropwise over 1 hour. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and the mixture was further stirred for 60 minutes. The polybenzoxazole precursor resin was then precipitated in 6 liters of water and the water-polybenzoxazole precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polybenzoxazole precursor resin was obtained by filtration, stirred again in 6 liters of water for 30 minutes and filtered again. Then, the obtained polybenzoxazole precursor resin was dried under reduced pressure at 45 ° C. for 3 days. The obtained polybenzoxazole precursor A-4 had a weight average molecular weight of 21,500 and a number average molecular weight of 9,500.
〔4,4’-オキシジフタル二酸無水物、4,4’-ジアミノジフェニルエーテル、及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-5:ラジカル重合性基を有するポリイミド前駆体)の合成〕
4,4’-オキシジフタル酸二無水物(ODPA)155.1gを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)134.0g及びγ-ブチロラクトン400mlを加えた。室温下で撹拌しながら、ピリジン79.1gを加えることにより、反応混合物を得た。反応による発熱の終了後、室温まで放冷し、更に16時間静置した。 <Synthesis example 5>
[Synthesis of polyimide precursor (A-5: polyimide precursor having radical polymerizable group) from 4,4'-oxydiphthaldioic anhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate]
155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine with stirring at room temperature. After the exotherm by the reaction was completed, the mixture was allowed to cool to room temperature and allowed to stand for another 16 hours.
〔3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、4,4’-ジアミノジフェニルエーテル、及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-6:ラジカル重合性基を有するポリイミド前駆体)の合成〕
合成例5において、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5に記載の方法と同様にして反応を行うことにより、ポリマーA-6を得た。このポリマーA-6の重量平均分子量(Mw)を測定したところ、22,000であった。 <Synthesis example 6>
[3,3', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and polyimide precursor from 2-hydroxyethyl methacrylate (A-6: Polyimide having a radically polymerizable group) Synthesis of precursor)]
Synthesis Example 5 except that 147.1 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride was used in place of 155.1 g of 4,4'-oxydiphthalic acid dianhydride. Polymer A-6 was obtained by carrying out the reaction in the same manner as in the method described in 5. The weight average molecular weight (Mw) of this polymer A-6 was measured and found to be 22,000.
撹拌機、及び、コンデンサーを取りつけたフラスコに、イミダゾール 30.0g(0.44モル)を脱水テトラヒドロフラン125mLに溶解し、10℃以下になるまで冷却した。続いて、ベンジルクロライド 28.1g(0.2モル)を1時間かけて滴下し、20~25℃に昇温した。20~25℃で3時間撹拌した後、発生した塩をろ紙でろ過し、ろ液を回収した。ろ液中のテトラヒドロフランを留去した後、300mLの酢酸エチルに溶解し、分液ロートに移した。次いで、これを100mLの水で2回、150mLの飽和食塩水で2回洗浄し、硫酸ナトリウムで乾燥した。これをろ紙でろ過しながら1口フラスコに移し、エバポレーターで溶媒を除去し、BG-1を33g得た。BG-1である事は、1H-NMRスペクトルから確認した。
1H-NMRデータを以下に示す。
1H-NMRデータ:(重DMSO、400MHz、内部標準:テトラメチルシラン)
δ(ppm)=7.17(s、1H)、7.61~7.65(t、2H)、7.69(s、1H)、7.74~7,78(t、1H)、7.83~7.85(d、2H)、8.20(s、1H) <Synthesis Example 7: Synthesis of Specific Compound BG-1>
In a flask equipped with a stirrer and a condenser, 30.0 g (0.44 mol) of imidazole was dissolved in 125 mL of dehydrated tetrahydrofuran and cooled to 10 ° C. or lower. Subsequently, 28.1 g (0.2 mol) of benzyl chloride was added dropwise over 1 hour, and the temperature was raised to 20 to 25 ° C. After stirring at 20 to 25 ° C. for 3 hours, the generated salt was filtered through a filter paper, and the filtrate was collected. Tetrahydrofuran in the filtrate was distilled off, dissolved in 300 mL of ethyl acetate, and transferred to a separating funnel. It was then washed twice with 100 mL of water and twice with 150 mL of saturated brine and dried over sodium sulfate. This was transferred to a 1-neck flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 33 g of BG-1. The fact that it was BG-1 was confirmed from 1 1 H-NMR spectrum.
1 1 H-NMR data is shown below.
1 1 H-NMR data: (heavy DMSO, 400 MHz, internal standard: tetramethylsilane)
δ (ppm) = 7.17 (s, 1H), 7.61 to 7.65 (t, 2H), 7.69 (s, 1H), 7.74 to 7,78 (t, 1H), 7 .83-7.85 (d, 2H), 8.20 (s, 1H)
撹拌機、及び、コンデンサーを取りつけたフラスコに、トリアゾール 30.4g(0.44モル)を脱水テトラヒドロフラン 200mLに溶解し、10℃以下になるまで冷却した。続いて、ベンジルクロライド 28.1g(0.2モル)を1時間かけて滴下し、20~25℃に昇温した。20~25℃で3時間撹拌した後、発生した塩をろ紙でろ過し、ろ液を回収した。ろ液中のテトラヒドロフランを留去した後、300mLの酢酸エチルに溶解し、分液ロートに移した。次いで、これを100mLの水で2回、150mLの飽和食塩水で2回洗浄し、硫酸ナトリウムで乾燥した。これをろ紙でろ過しながら1口フラスコに移し、エバポレーターで溶媒を除去し、BG-2を31g得た。BG-2である事は、1H-NMRスペクトルから確認した。
1H-NMRデータを以下に示す。
1H-NMRデータ:(重DMSO、400MHz、内部標準:テトラメチルシラン)
δ(ppm)=7.76~7.64(t、2H)、7.75~7,79(t、1H)、8.07~8.10(d、2H)、8.38(s、1H)、9.44(s、1H) <Synthesis Example 8: Synthesis of Specific Compound BG-2>
In a flask equipped with a stirrer and a condenser, 30.4 g (0.44 mol) of triazole was dissolved in 200 mL of dehydrated tetrahydrofuran and cooled to 10 ° C. or lower. Subsequently, 28.1 g (0.2 mol) of benzyl chloride was added dropwise over 1 hour, and the temperature was raised to 20 to 25 ° C. After stirring at 20 to 25 ° C. for 3 hours, the generated salt was filtered through a filter paper, and the filtrate was collected. Tetrahydrofuran in the filtrate was distilled off, dissolved in 300 mL of ethyl acetate, and transferred to a separating funnel. It was then washed twice with 100 mL of water and twice with 150 mL of saturated brine and dried over sodium sulfate. This was transferred to a 1-neck flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 31 g of BG-2. The fact that it was BG-2 was confirmed from 1 1 H-NMR spectrum.
1 1 H-NMR data is shown below.
1 1 H-NMR data: (heavy DMSO, 400 MHz, internal standard: tetramethylsilane)
δ (ppm) = 7.76 to 7.64 (t, 2H), 7.75 to 7,79 (t, 1H), 8.07 to 8.10 (d, 2H), 8.38 (s, 1H), 9.44 (s, 1H)
撹拌機、及び、コンデンサーを取りつけたフラスコに、イミダゾール 28.6g(0.42モル)を脱水テトラヒドロフラン 125mLに溶解し、10℃以下になるまで冷却した。続いて、イソフタル酸ジクロリド 20.3g(0.1モル)を脱水テトラヒドロフラン80mLに溶解し、1時間かけて滴下し、20~25℃に昇温した。20~25℃で3時間撹拌した後、発生した塩をろ紙でろ過し、ろ液を回収した。ろ液中のテトラヒドロフランをエバポレーターで除去し、40mLのBG-3を脱水テトラヒドロフランに溶解し、-5℃で1日静置した。発生した結晶をろ過し、テトラヒドロフラン30mLでかけ洗いし、25℃で3時間真空乾燥し、BG-3を15g得た。BG-3である事は、1H-NMRスペクトルから確認した。
1H-NMRデータを以下に示す。
1H-NMRデータ:(重DMSO、400MHz、内部標準:テトラメチルシラン)
δ(ppm)=7.18(s、2H)、7.77(s、2H)、7.82~7.86(t、1H)、8.15~8.17(d、2H)、8.18(s、1H)、8.30(s、1H) <Synthesis Example 9: Synthesis of Specific Compound BG-3>
In a flask equipped with a stirrer and a condenser, 28.6 g (0.42 mol) of imidazole was dissolved in 125 mL of dehydrated tetrahydrofuran and cooled to 10 ° C. or lower. Subsequently, 20.3 g (0.1 mol) of isophthalic acid dichloride was dissolved in 80 mL of dehydrated tetrahydrofuran, added dropwise over 1 hour, and the temperature was raised to 20 to 25 ° C. After stirring at 20 to 25 ° C. for 3 hours, the generated salt was filtered through a filter paper, and the filtrate was collected. Tetrahydrofuran in the filtrate was removed by an evaporator, 40 mL of BG-3 was dissolved in dehydrated tetrahydrofuran, and the mixture was allowed to stand at −5 ° C. for 1 day. The generated crystals were filtered, washed with 30 mL of tetrahydrofuran, and vacuum dried at 25 ° C. for 3 hours to obtain 15 g of BG-3. The fact that it was BG-3 was confirmed from 1 1 H-NMR spectrum.
1 1 H-NMR data is shown below.
1 1 H-NMR data: (heavy DMSO, 400 MHz, internal standard: tetramethylsilane)
δ (ppm) = 7.18 (s, 2H), 7.77 (s, 2H), 7.82 to 7.86 (t, 1H), 8.15 to 8.17 (d, 2H), 8 .18 (s, 1H), 8.30 (s, 1H)
撹拌機、及び、コンデンサーを取りつけたフラスコに、トリアゾール 15.2g(0.22モル)を塩化メチレン 150mLと混合し、10℃以下になるまで冷却した。続いて、メタクリル酸クロリド 10.5g(0.1モル)を1時間かけて滴下し、20~25℃に昇温した。20~25℃で3時間撹拌した後、塩化メチレンを200mL加え、発生した塩をろ紙でろ過し、ろ液を回収した。ろ液を分液ロートに移し、水50mLで2回、150mLの飽和食塩水で2回洗浄し、硫酸ナトリウムで乾燥した。これをろ紙でろ過しながら1口フラスコに移し、エバポレーターで溶媒を除去し、BG-4を12g得た。BG-4である事は、1H-NMRスペクトルから確認した。
1H-NMRデータを以下に示す。
1H-NMRデータ:(重クロロホルム、400MHz、内部標準:テトラメチルシラン)
δ(ppm)=2.17(s、3H)、6.09(s、1H)、6.44(s、1H)、8.06(s、1H)、8.95(s、1H) <Synthesis Example 10: Synthesis of Specific Compound BG-4>
In a flask equipped with a stirrer and a condenser, 15.2 g (0.22 mol) of triazole was mixed with 150 mL of methylene chloride and cooled to 10 ° C. or lower. Subsequently, 10.5 g (0.1 mol) of methacrylic acid chloride was added dropwise over 1 hour, and the temperature was raised to 20 to 25 ° C. After stirring at 20 to 25 ° C. for 3 hours, 200 mL of methylene chloride was added, and the generated salt was filtered through a filter paper to recover the filtrate. The filtrate was transferred to a separatory funnel, washed twice with 50 mL of water and twice with 150 mL of saturated brine, and dried over sodium sulfate. This was transferred to a 1-neck flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 12 g of BG-4. The fact that it was BG-4 was confirmed from 1 1 H-NMR spectrum.
1 1 H-NMR data is shown below.
1 1 H-NMR data: (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane)
δ (ppm) = 2.17 (s, 3H), 6.09 (s, 1H), 6.44 (s, 1H), 8.06 (s, 1H), 8.95 (s, 1H)
上述の特定化合物BG-1~BG-4と同様の方法により、BG-5~BG-18を合成した。 <Synthesis of specific compounds BG-5 to BG-16>
BG-5 to BG-18 were synthesized by the same method as the above-mentioned specific compounds BG-1 to BG-4.
各実施例において、それぞれ、下記表1又は表2に記載の成分を混合し、各硬化性樹脂組成物を得た。また、各比較例において、それぞれ、下記表2に記載の成分を混合し、各比較用組成物を得た。
具体的には、表1又は表2に記載の成分の含有量は、表1又は表2の「質量部」に記載の量とした。
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1又は表2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, the components shown in Table 1 or Table 2 below were mixed to obtain each curable resin composition. Further, in each comparative example, the components shown in Table 2 below were mixed to obtain each comparative composition.
Specifically, the content of the component shown in Table 1 or Table 2 was the amount shown in "Mass part" of Table 1 or Table 2.
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 Table 1 or Table 2, the description of "-" indicates that the composition does not contain the corresponding component.
・A-1~A-6:上記で合成したA-1~A-6
実施例25においては、A-5を16.9質量部、A-6を16.9質量部、それぞれ使用した。 [Heterocycle-containing polymer precursor]
-A-1 to A-6: A-1 to A-6 synthesized above
In Example 25, 16.9 parts by mass of A-5 and 16.9 parts by mass of A-6 were used.
・BG-1~BG-18:上記で合成したBG-1~BG-18
・B-1~B-2:下記構造の化合物。B-1~B-2は、いずれも式(1-1)で表される構造を有しておらず、特定化合物には該当しない。
BG-1 to BG-18: BG-1 to BG-18 synthesized above
-B-1 to B-2: Compounds having the following structures. None of B-1 to B-2 has a structure represented by the formula (1-1) and does not correspond to a specific compound.
・DMSO:ジメチルスルホキシド
・GBL:γ-ブチロラクトン
・NMP:N-メチルピロリドン
表1又は表2中、DMSO/GBLの記載は、DMSOとGBLをDMSO:GBL=60:40(質量比)の割合で混合したことを示している。
表1又は表2中、NMP/乳酸エチルの記載は、N-メチルピロリドンと乳酸エチルをN-メチルピロリドン:乳酸エチル=80:20(質量比)の割合で混合したことを示している。 〔solvent〕
-DMSO: dimethyl sulfoxide-GBL: γ-butyrolactone-NMP: N-methylpyrrolidone In Table 1 or Table 2, DMSO / GBL is described as DMSO and GBL in the ratio of DMSO: GBL = 60: 40 (mass ratio). It shows that it was mixed.
In Table 1 or Table 2, the description of NMP / ethyl lactate indicates that N-methylpyrrolidone and ethyl lactate were mixed in a ratio of N-methylpyrrolidone: ethyl lactate = 80:20 (mass ratio).
・OXE-01:IRGACURE OXE 01(BASF社製)
・OXE-02:IRGACURE OXE 02(BASF社製) [Photopolymerization initiator]
・ OXE-01: IRGACURE OXE 01 (manufactured by BASF)
-OXE-02: IRGACURE OXE 02 (manufactured by BASF)
・SR-209:SR-209(サートマー社製)
・SR-231:SR-231(サートマー社製)
・SR-239:SR-239(サートマー社製)
・A-DPH:ジペンタエリスリトールヘキサアクリレート(新中村化学工業(株)製) [Polymerizable compound]
-SR-209: SR-209 (manufactured by Sartmer)
-SR-231: SR-231 (manufactured by Sartmer)
-SR-239: SR-239 (manufactured by Sartmer)
・ A-DPH: Dipentaerythritol hexaacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
・F-1:1,4-ベンゾキノン
・F-2:4-メトキシフェノール
・F-3:1,4-ジヒドロキシベンゼン
・F-4:2-ニトロソ-1-ナフト-ル(東京化成工業(株)製) [Polymerization inhibitor]
・ F-1: 1,4-benzoquinone ・ F-2: 4-methoxyphenol ・ F-3: 1,4-dihydroxybenzene ・ F-4: 2-nitroso-1-naphthol (Tokyo Chemical Industry Co., Ltd.) ) Made)
・G-1:下記化合物
・G-2:下記化合物
・G-3:下記化合物
・G-4:下記化合物
Etはエチル基を表す。
-G-1: The following compound-G-2: The following compound-G-3: The following compound-G-4: The following compound Et represents an ethyl group.
・H-1:1H-テトラゾール
・H-2:1,2,4-トリアゾール
・H-3:5-フェニルテトラゾール [Migration inhibitor]
・ H-1: 1 H-tetrazole ・ H-2: 1,2,4-triazole ・ H-3: 5-phenyltetrazole
・I-1~I-3:下記構造の化合物
-I-1 to I-3: Compounds having the following structure
・J-1:N-フェニルジエタノールアミン(東京化成工業(株)製) 〔Additive〕
・ J-1: N-Phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
〔膜強度(破断伸び)の評価〕
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の厚さの均一な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全面に対して、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーでi線露光した。
上記露光後の硬化性樹脂組成物層(樹脂層)を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、表1又は表2の「硬化温度(℃)」の欄に記載の温度に達した後、3時間加熱した。硬化後の樹脂層(硬化膜)を4.9質量%フッ化水素酸水溶液に浸漬し、シリコンウェハから硬化膜を剥離した。剥離した硬化膜を、打ち抜き機を用いて打ち抜いて、試料幅3mm、試料長30mmの試験片を作製した。得られた試験片を、引張り試験機(テンシロン)を用いて、クロスヘッドスピード300mm/分で、25℃、65%RH(相対湿度)の環境下にて、JIS-K6251に準拠してフィルムの長手方向の破断伸び率を測定した。評価は各5回ずつ実施し、フィルムが破断した時の伸び率(破断伸び率)について、その算術平均値を指標値として用いた。
上記指標値を下記評価基準に従って評価し、評価結果は表1又は表2の「膜強度」の欄に記載した。上記指標値が大きいほど、得られる硬化膜の膜強度(破断伸び)に優れるといえる。 <Evaluation>
[Evaluation of film strength (break elongation)]
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 uniform curable resin composition layer having a thickness of about 15 μm on the silicon wafer.
The entire surface of the obtained curable resin composition layer was exposed to i-rays with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).
The curable resin composition layer (resin layer) after the above exposure is heated at a heating rate of 10 ° C./min under a nitrogen atmosphere, and is displayed in the “Curing temperature (° C.)” column of Table 1 or Table 2. After reaching the stated temperature, it was heated for 3 hours. The cured resin layer (cured film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured film was peeled off from the silicon wafer. The peeled cured film was punched out using a punching machine to prepare a test piece having a sample width of 3 mm and a sample length of 30 mm. The obtained test piece was subjected to a film in accordance with JIS-K6251 using a tensile tester (Tencilon) at a crosshead speed of 300 mm / min and in an environment of 25 ° C. and 65% RH (relative humidity). The elongation at break in the longitudinal direction was measured. The evaluation was carried out 5 times each, and the arithmetic mean value of the elongation rate (break elongation rate) when the film was broken was used as an index value.
The above index values were evaluated according to the following evaluation criteria, and the evaluation results were described in the “Film strength” column of Table 1 or Table 2. It can be said that the larger the index value is, the better the film strength (break elongation) of the obtained cured film is.
A:上記指標値が60%以上であった。
B:上記指標値が55%以上60%未満であった。
C:上記指標値が50%以上55%未満であった。
D:上記指標値が50%未満であった。 -Evaluation criteria-
A: The above index value was 60% or more.
B: The index value was 55% or more and less than 60%.
C: The above index value was 50% or more and less than 55%.
D: The above index value was less than 50%.
-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 storage stability (membrane change rate)]
-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 of the Examples and Comparative Examples, 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 layer was formed by applying it on a silicon wafer by a spin coating method using the same rotation speed as in the case of. 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1又は表2の「保存安定性」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 listed in the "Storage stability" column of Table 1 or Table 2. 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20%未満であった。
D:上記膜厚変化率が20%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 and less than 20%.
D: The film thickness change rate was 20% or more.
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シリコンウェハ上にスピンコート法により適用し、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15μmの均一な厚さの硬化性樹脂組成物層を形成した。シリコンウェハ上の硬化性樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーでi線露光し、露光した硬化性樹脂組成物層(樹脂層)を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、表1又は表2に記載の温度で3時間加熱して、硬化性樹脂組成物層の硬化層(樹脂層)を得た。
得られた樹脂層について下記の薬液に下記の条件で浸漬し、溶解速度を算定した。
薬液:ジメチルスルホキシド(DMSO)と25質量%のテトラメチルアンモニウムヒドロキシド(TMAH)水溶液の90:10(質量比)の混合物
評価条件:樹脂層を上記薬液に75℃で15分間浸漬して前後の膜厚を比較し、溶解速度(nm/分)を算出した。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。
評価は下記評価基準に従って行い、評価結果は表1又は表2の「耐薬品性」の欄に記載した。溶解速度の値が小さいほど、得られる硬化膜(樹脂層)は耐薬品性に優れるといえる。 [Evaluation of chemical resistance (membrane change rate)]
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 form a curable resin composition layer having a uniform thickness of 15 μm on the silicon wafer. The curable resin composition layer on the silicon wafer was i-line-exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed curable resin composition layer (resin layer) was subjected to i-line exposure. A cured layer (resin layer) of a curable resin composition layer was obtained by heating in a nitrogen atmosphere at a heating rate of 10 ° C./min and heating at the temperatures shown in Table 1 or 2 for 3 hours. ..
The obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
Chemical solution: A mixture of dimethyl sulfoxide (DMSO) and a 25 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 90:10 (mass ratio) Evaluation conditions: The resin layer is immersed in the above chemical solution at 75 ° C. for 15 minutes before and after. The film thicknesses were compared and the dissolution rate (nm / min) was calculated. 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 evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the "Chemical resistance" column of Table 1 or Table 2. It can be said that the smaller the value of the dissolution rate, the better the chemical resistance of the obtained cured film (resin layer).
A:溶解速度が200nm/分未満であった。
B:溶解速度が200nm/分以上300nm/分未満であった。
C:溶解速度が300nm/分以上400nm/分未満であった。
D:溶解速度が400nm/分以上であった。 -Evaluation criteria-
A: The dissolution rate was less than 200 nm / min.
B: The dissolution rate was 200 nm / min or more and less than 300 nm / min.
C: The dissolution rate was 300 nm / min or more and less than 400 nm / min.
D: The dissolution rate was 400 nm / min or more.
比較例1~比較例5に係る硬化性樹脂組成物は、特定化合物を含有しない。この比較例1~比較例5に係る硬化性樹脂組成物は、硬化膜の膜強度及び組成物の保存安定性の少なくとも一方に劣ることが分かる。 From the above results, it can be seen that the heterocyclic polymer precursor and the curable resin composition containing the specific compound according to the present invention are excellent in the film strength of the cured film and the storage stability of the composition.
The curable resin compositions according to Comparative Examples 1 to 5 do not contain a specific compound. It can be seen that the curable resin compositions according to Comparative Examples 1 to 5 are inferior to at least one of the film strength of the cured film and the storage stability of the composition.
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で行った。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). Exposure was performed at a wavelength of 365 nm via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 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 (15)
- ポリイミド前駆体、ポリアミドイミド前駆体、及び、ポリベンゾオキサゾール前駆体よりなる群から選ばれた少なくとも1種の樹脂、並びに、
下記式(1-1)で表される構造を有する化合物を含む
硬化性樹脂組成物。
A curable resin composition containing a compound having a structure represented by the following formula (1-1).
- 前記式(1-1)におけるArが5員環構造である、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 Ar in the formula (1-1) has a 5-membered ring structure.
- 前記式(1-1)で表される構造が、下記式(1-2)で表される構造である、請求項1又は2に記載の硬化性樹脂組成物。
- 前記式(1-1)で表される構造を有する化合物が、下記式(1-3)で表される化合物である、請求項1~3のいずれか1項に記載の硬化性樹脂組成物。
- 前記X1が芳香族炭化水素環構造を含む、請求項4に記載の硬化性樹脂組成物。 The curable resin composition according to claim 4, wherein X 1 contains an aromatic hydrocarbon ring structure.
- 前記式(1-1)で表される構造を有する化合物の分子量が、90~500である、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, wherein the compound having the structure represented by the formula (1-1) has a molecular weight of 90 to 500.
- 前記式(1-1)で表される構造を有する化合物が、熱塩基発生剤である、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 compound having the structure represented by the formula (1-1) is a thermosetting agent.
- 光重合開始剤、及び、重合性化合物を更に含む、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, further comprising a photopolymerization initiator and a polymerizable compound.
- 再配線層用層間絶縁膜の形成に用いられる、請求項1~8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 8, which is used for forming an interlayer insulating film for a rewiring layer.
- 請求項1~9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 9.
- 請求項10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 10 and containing a metal layer between any of the cured films.
- 請求項1~9のいずれか1項に記載の硬化性樹脂組成物を基材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 9 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12に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 12, further comprising an exposure step for exposing the film and a developing step for developing the film.
- 前記膜を50~450℃で加熱する加熱工程を含む、請求項12又は13に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 12 or 13, which comprises a heating step of heating the film at 50 to 450 ° C.
- 請求項10に記載の硬化膜又は請求項11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 10 or the laminate according to claim 11.
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